Polypropylene-Based Adhesive Compositions

ABSTRACT

An adhesive blend is described that can include a semi-crystalline copolymer of propylene and at least one comonomer selected from the group consisting of ethylene and at least one C 4  to C 20  α-olefin, the copolymer having a weight average molecular weight (Mw) from about 15,000 to about 200,000; an melt index (MI) from about 7 dg/min to about 3000 dg/min as measured by ASTM D 1238(B), and a (Mw/Mn) of approximately 2. Various production processes are also described. Also described are adhesive compositions and methods for making adhesive compositions having polymers or polymer blends with melt flow rates (MFRs) equal to and above 250 dg/min. at 230 NC. Certain specific embodiments of the invention involve the use of a free radical initiator, e.g., a peroxide.

RELATED APPLICATIONS

This application is a continuation of Ser. No. 10/720,512 which is adivisional application of Ser. No. 09/745,394, filed Dec. 21, 2000, nowallowed, that claims the benefit of Ser. No. 60/171,715, filed Dec. 22,1999, and Ser. No. 60/199,093, filed Apr. 21, 2000, the disclosures ofwhich are fully incorporated by reference.

FIELD OF INVENTION

The present invention relates to the use of propylene copolymers inadhesive applications. A specific embodiment of the invention isdirected to copolymers of propylene and ethylene or propylene and atleast one C₄ to C₂₀ α-olefin, preferably a C₄ to C₈ α-olefin where thepropylene is the predominant monomer and the copolymer issemi-crystalline. Another specific embodiment of the invention relatesto adhesive compositions and methods for making adhesive compositionswith polymers or polymer blends having melt flow rates (MFRs) of 250dg/min. at 230 NC and higher. Certain specific embodiments of theinvention involve the use of a free radical initiator, e.g., a peroxide.

BACKGROUND

Hot-melt adhesives are thermoplastic materials that can be heated to amelt and then applied to various substrates. A bond is formed uponcooling and resolidification. Among the most widely used thermoplasticpolymers in hot-melt adhesives is ethylene-vinyl acetate copolymer(“EVA”) which is combined with a variety of plasticizers, tackifiers,antioxidants, waxes, and extenders for purposes of improving and/orcontrolling the viscosity, adhesive properties, shelf-life, stabilityand cost. Plasticizers have typically included such compounds aspolybutenes and phthalates, tackifiers have typically included suchcompositions as rosin esters and hydrocarbon resins, antioxidants arefrequently based upon the known hindered phenol compounds, and wax helpsto reduce the melt viscosity in addition to reducing costs.

These hot-melt adhesives have the drawback of often becoming brittlebelow the glass-transition temperature. Historically, ethylene basedsemi-crystalline polymers like polyethylene and ethylene vinyl acetate(EVA), have been used in various adhesive applications; however, suchpolymers have many problems in their end use applications. For example,semi-crystalline linear low density polyethylene (LLDPE) can be used inhot melt adhesive applications where the crystalline network formed oncooling makes a good adhesive free of tack, but the high level ofcrystallinity causes the material to be brittle. For this reason othermonomers, such as vinyl acetate (VA), or alpha-olefins are oftenco-polymerized with ethylene to break up some of the crystallinity andsoften the adhesive. Thus the use of hot-melt adhesives based upon EVAis limited when low temperature conditions of use are desired.

Styrene block copolymers (“SBC”) are independently known as an importantclass of base polymers for adhesive compositions, particularly for suchuses as in hot melt pressure sensitive adhesives in tapes, label stock,diaper assembly and the like. However, because of higher meltviscosities than EVA based compositions, SBC based adhesive compositionsare not typically used for packaging where high-speed application iseconomically desirable.

Certain adhesive composition blends of SBC and EVA are known, eventhough the base polymers are largely incompatible, in the sense of notbeing able to form stable blends largely free of separation orstratification and resulting nonuniformity of properties. U.S. Pat. No.4,345,349 describes book-binding hot-melt adhesive compositions preparedfrom 15-30% SBC, 5-10% EVA, 25-40% rosin ester tackifier, 25-35% waxdiluent and 0.5-3% of a stabilizer, e.g., hindered phenol compound. Theratio of SBC to the ethylene vinyl acetate copolymer is from 1.75/1 to6/1. The low-temperature flexibility improves by increasing the amountof SBC in the composition and using a high softening point tackifier orhigh melting point wax shortens setting speed. Setting time, in order tobe useful in the described bookbinding process, is to be within 30seconds, and times within 26 seconds are exemplified. U.S. Pat. No.4,394,915 describes a hot melt adhesive particularly suitable forpolyethylene-terepthalate bottle assemblies comprising typically 20-40%SBC, 5-20% EVA, 30-60% tackifying resin, 10-30% wax or oil, and 0.1-4%stabilizer. The tackifying resin can be any of a number of availablerosins or resins, including the aliphatic petroleum resins, but ispreferably a polymerized tall oil rosin.

PCT/US97/04161 teaches the use of ethylene based copolymers as hot meltadhesive and these materials are useful in some applications, but sufferin that they have higher melt viscosity, poorer processing and pooreradhesion to some types of surfaces than propylene based copolymers. U.S.Pat. No. 5,118,762 addresses the industrial need for hot melt adhesivesthat have a low melt viscosity and high temperature resistance to shear.The solution in this document is the use of a predominantly branchedstyrene-isoprene-styrene (SIS) triblock copolymer with a tackifyingresin that is compatible with the elastomeric isoprene block, e.g.,diene-olefin copolymer resins, rosin esters or saturated petroleumresins, e.g., hydrogenated dicyclopentadiene resins such as ESCOREZ®5000 series resins of the ExxonMobil Chemical Company.

Blends of isotactic polypropylene and ethylene propylene rubber are wellknown in the prior art, prior art Ziegler-Natta catalyst systems couldonly produce ethylene propylene rubber compositions with greater than30% by weight ethylene at practical, economic polymerization conditions.There exists a need for polymeric materials which have advantageousprocessing characteristics while still providing suitable end propertiesto articles formed therefrom, e.g., tensile and impact strength.Copolymers and blends of polymers have been developed to try and meetthe above needs. U.S. Pat. No. 3,882,197 to Fritz et al. describesblends of stereoregular propylene/alpha-olefin copolymers, stereoregularpropylene, and ethylene copolymer rubbers. In U.S. Pat. No. 3,888,949Chi-Kai Shih, assigned to E I DuPont, shows the synthesis of blendcompositions containing isotactic polypropylene and copolymers ofpropylene and an alpha-olefin, containing between 6-20 carbon atoms,which have improved elongation and tensile strength over either thecopolymer or isotactic polypropylene. Copolymers of propylene andalpha-olefin are described wherein the alpha-olefin is hexene, octene ordodecene. However, the copolymer is made with a heterogeneous titaniumcatalyst which makes copolymers which are non-uniform in compositionaldistribution and typically broad in molecular weight distribution.Compositional distribution is a property of copolymers where thereexists statistically significant intermolecular or intramoleculardifference in the composition of the polymer.

In U.S. Pat. No. 4,461,872, A. C. L. Su improved on the properties ofthe blends described in U.S. Pat. No. 3,888,949 by using anotherheterogeneous catalyst system. However, the properties and compositionsof the copolymer with respect to either the nature and type of monomers(alpha-olefin containing 6-20 carbon atoms) or the blocky heterogeneousintra/inter molecular distribution of the alpha-olefin in the polymerhave not been resolved since the catalysts used for these polymerizationof propylene and alpha-olefin are expected to form copolymers which havestatistically significant intermolecular and intramolecularcompositional differences.

In two successive publications in the journal of Macromolecules, 1989, v22, pages 3851-3866, J. W. Collette of E. I. DuPont has described blendsof isotactic polypropylene and partially atactic polypropylene whichhave desirable tensile elongation properties. However, the partiallyatactic propylene has a broad molecular weight distribution as shown inFIG. 8 of the first publication. The partially atactic polypropylene isalso composed of several fractions, which differ in the level oftacticity of the propylene units as shown by the differences in thesolubility in different solvents. This is shown by the correspondingphysical decomposition of the blend which is separated by extractionwith different solvents to yield individual components of uniformsolubility characteristics as shown in Table IV of the abovepublications.

In U.S. Pat. Nos. 3,853,969 and 3,378,606, E. G. Kontos discloses theformation of in situ blends of isotactic polypropylene and “stereoblock” copolymers of propylene and another olefin of 2 to 12 carbonatoms, including ethylene and hexene. The copolymers of this inventionare necessarily heterogeneous in intermolecular and intramolecularcomposition distribution. This is demonstrated by the synthesisprocedures of these copolymers which involve sequential injection ofmonomer mixtures of different compositions to synthesize polymericportions of analogously different compositions. In addition, FIG. 1 ofboth patents shows that the “stereo block” character, which is intra orintermolecular compositional differences in the context of thedescription of the present invention, is essential to the benefit of thetensile and elongation properties of the blend. In situ blends ofisotactic polypropylene and compositionally uniform random ethylenepropylene copolymers have poor properties.

Amorphous polyolefins, such as atactic polypropylene, have nocrystalline network and thus have poor cohesive strength. To improvecohesive strength high molecular weight amorphous polyolefins are neededin high concentrations and this leads to high viscosity and poorprocessability.

Moreover, all of these compositions either do not meet all of thedesired properties for various applications, and/or involve costly andburdensome process steps to achieve the desired results. It is alsodesirable in packaging to have adhesive compositions that have suitablylow melt viscosity for high speed automated coating processes, asufficiently long time before hardening to preserve sufficient adhesion(known in industry as “open time”) in assembly operations such as boxclosures, yet a quick enough setting speed to allow shortest timeapplication of adhering pressure (known in industry as “setting time”).

As set forth in greater detail below, certain aspects of this inventionrelate to the use of a peroxide or other free-radical initiator toprovide a modified polymer or polymer blend. The use of peroxide todegrade certain polymers has been published in the literature.

For example, peroxide-initiated degradation of certain polypropyleneresins is discussed generally in the article by Tzoganakis, et al.,entitled “Production of Controlled-Rheology Polypropylene Resins byPeroxide Promoted Degradation During Extrusion,” pp. 170-180, PolymerEngineering and Science, Vol. 28, No. 3 (1988), and in the article byRosales, et al, entitled “Viscoelastic Behavior of Controlled-RheologyPolypropylene Resins,” pp. 153-169, Materials Engineering, Vol. 4, No. 2(1993).

Gahleitner et al., U.S. Pat. No. 5,705,568, relates to chemicallydegraded block copolymers. That patent discusses the use of peroxides todegrade elastic polypropylene homopolymers and copolymers withstereoregular block arrangements, blocks of isotactic and atacticpropylene sequences. The patent discloses using minor amounts ofperoxide, from 0.001 to 0.8% by weight, preferably 0.05% to 0.5% byweight to raise the melt flow index (MFI). The patent also discloses theaddition of fillers, stabilizers and mould release agents. However, thispatent does not discuss adhesive compositions.

Peroxides have also been used to oxidatively degrade olefinic polymersand/or polymer blends useful as lubricant compositions, as discussed,for example, in Gordon et al., U.S. Pat. No. 4,743,391 and Chung et al.,U.S. Pat. No. 4,749,505.

Peroxides have also been used as curing agents in elastomeric blends.Duncan, U.S. Pat. No. 4,143,099, for example, discusses the use ofperoxides in curing and “semi-curing” elastomeric blends, by adding theperoxide curing agent while masticating and shearing the mixture ofpolymers, and completing the semi-curing of the polymers before theonset of melting.

The present invention is directed in general to providing improvedadhesive compositions, and processes or methods for making suchcompositions.

SUMMARY

One or more specific embodiments of the present invention relates to anadhesive blend comprising a semi-crystalline copolymer of propylene andat least one comonomer selected from the group consisting of ethyleneand at least one C₄ to C₂₀ α-olefin, the copolymer having a weightaverage molecular weight (Mw) from about 15,000 to about 200,000; anmelt index (MI) from about 7 dg/min to about 3000 dg/min, and a (Mw/Mn)of approximately 2.

Other specific embodiments relate to a polymerization processcomprising: reacting propylene and at least one comonomer selected fromthe group consisting of ethylene and at least one C₄ to C₂₀ α-olefin,under polymerization conditions in the presence of a metallocenecatalyst capable of incorporating the propylene sequences into isotacticor syndiotactic orientations, in at least one reactor to produce a firstcopolymer having at least 65 mole % propylene and wherein preferably atleast 40% of the propylene sequences are in isotactic or syndiotacticorientations; wherein the copolymer has a melt index (MI) from about 7dg/min to about 3000 dg/min.

Still further embodiments relate to articles of manufacture comprisingthe aforementioned compositions or other compositions disclosed herein.The article of manufacture may be a sanitary article, such as a diaper,feminine hygiene article and so forth.

Certain specific embodiments of the invention relate to adhesivecompositions that include a polymer or blend of polymers in which thepolymer or blend of polymers themselves have an MFR greater than about250 g/10 min. at 230 NC, and processes for making such adhesivecompositions. It is understood that while the overall composition mayinclude additional ingredients that may further increase the overall MFRof the composition, it is the MFR of the actual polymer or polymer blenditself that is referred to herein. Advantageously, therefore, additionaltreatment steps, e.g., post-extrusion, or MFR-increasing additives arenot necessarily required, since the polymer or blend of polymers itselfpossesses the desired MFR. Preferably, the polymer or polymer blend hasa melting point of from 60 to 120 degrees C., more preferably from 80 to100 degrees C. Also, the polymer or polymer blend preferably includesethylene (or an alpha olefin, e.g., having from 4-20 carbon atoms) inthe amount of up to 30 mole %, preferably from 3 mole % to 20 mole % andmore preferably from 7 mole % to 15 mole wt %. In this context, theethylene or alpha olefin can be units forming part of a randomsemicrystalline copolymer that includes both propylene units andethylene units, e.g., when a single copolymer is used (not a blend).Alternatively, a blend can be used in which isotactic polypropylene isblended with a polyethylene, in which case the ethylene units in thepolyethylene should be up to 30 mole % of the overall polymer blend. Asdiscussed in greater detail below, it is contemplated that while thepresence of ethylene units may provide the desired melting point, thosesame ethylene units may cause crosslinking to such an extent that theMFR is decreased rather than increased, and for that reason, the amountof ethylene should be limited.

In other specific embodiments, adhesive compositions are describedcontaining polymers or polymer blends having an MFR greater than about250 dg/min. at 230 NC, wherein the composition preferably includes arandom copolymer produced by copolymerizing propylene and at least oneof ethylene or alpha-olefin having 20 or less carbon atoms, preferably 8or less carbon atoms, the random copolymer having a crystallinity atleast about 2% and no greater than about 65% derived from stereoregularpolypropylene sequences and a melting point of from about 25 NC to about105 NC. Preferably, the random copolymer has a melting point.

In still other specific embodiments, adhesive compositions aredescribed, which include the reaction product of a free radicalinitiator and a random copolymer produced by copolymerizing propyleneand at least one of ethylene or alpha-olefin having 8 or less carbonatoms, the random copolymer having a crystallinity at least about 2% andno greater than about 65% derived from stereoregular polypropylenesequences and a melting point of from about 25 NC to about 105 NC.Preferably, this reaction product has an MFR greater than about 250 g/10min. at 230 NC.

Yet another specific embodiment of this invention includes a randompolymer with a melting point between about 60 NC and 140 NC, morepreferably between 80 NC and 110 NC. The viscosity as measured by meltflow rate at 230 NC should be between 2 and 5600, more preferablybetween 70 and 370, and most preferably between 300 and 1800.Correspondingly, the melt index, measured at 190 NC, should be between20 and 1500, more preferably between 40 and 1000, and most preferablybetween 100 and 500. Further, the tensile elongation of the polymer atroom temperature should be in excess of 50%, more preferably in excessof 100%, and most preferably in excess of 300%. Preferably, the randomcopolymer is a low molecular weight copolymer containing propylene unitsin an amount of 80% or above, preferably more than 90%, with thepropylene units preferably being predominantly isotactic sequences (morethan 80% of the units being isotactic pentads), as measured by C-13 NMR.The random copolymers can have long chain branching, providing greaterflexibility for desired Theological properties.Still another specific embodiment of the invention includes a polyolefincomposition containing a physical blend, wherein an ethylene-propylenecopolymer is blended together with isotactic polypropylene. Thoseethylene-propylene copolymers are preferably derived by solutionpolymerization using chiral metallocene catalysts. Thoseethylene-propylene copolymers preferably have crystallinity derived fromisotactic propylene sequences. In those blend compositions, thecomposition of the copolymers includes up to 30 wt % and preferably upto 20 wt % ethylene. Those copolymers may be linear or branched. Thoseblends preferably contain substantial amounts of isotacticpolypropylene, at least about 5 to 10 wt %. In a specific embodiment,the blend can include isotactic polypropylene in an amount up to about50 wt %, or alternatively up to about 80 wt %. The blend can alsoinclude other olefin-based polymers, such as reactor copolymers andimpact copolymers. Desirably, the use of the blends described aboveprovide for favorable melting temperatures due to the presence of theisotactic polypropylene while providing a separate moleculararchitecture for the copolymer, thus improving the rheology, elasticityand flexibility of the adhesive composition.

Another specific embodiment of this invention relates to a process formaking a modified adhesive composition. For example, a process isdescribed that includes (a) providing a first polymer composition havingan MFR less than 250 dg/min. at 230 NC. and including a random copolymerproduced by copolymerizing propylene and at least one of ethylene oralpha-olefin having 8 or less carbon atoms, the random copolymer havinga crystallinity at least about 2% and no greater than about 65% derivedfrom stereoregular polypropylene sequences and a melting point of fromabout 25 NC to about 105 NC; and (b) contacting the first polymercomposition, in the melted state, with a free radical initiator, toprovide a second polymer composition, wherein the second polymercomposition has an MFR greater than 250 dg/min. at 230 NC.

A specific embodiment of a process for making an adhesive compositionutilizes chain scission to attain low molecular weight polymers frompolymers of much higher molecular weight. This chain scission proceduremay be used for both a composition that includes a random copolymer anda composition that includes a blend of the random copolymer and acrystalline polymer, e.g., isotactic polypropylene. The chain scissionprocedure may include heating the polymer, or polymer blend, to a moltenstate in the presence of a free radical initiator, i.e., an agentcapable of producing free radicals. In the case of a blend, the polymercomponents may both be simultaneously treated with the free radicalinitiator, to cause the desired level or degree of degradation.Alternatively, only one of the components may be treated with the freeradical initiator, to cause the desired level or degree of degradation,following which the other component may then be added after degradationhas begun or been completed. In either case, the temperature of thepolymer, or blend, should be sufficiently high when the initiator ispresent to maintain all of the components in the molten state. Thedegradation may be performed in any number of environments, usingconventional mixing procedures. When a batch mode is used, degradationshould be carried out in an intensive mixer such as a masticator or aBrabender mixer. When a continuous mode is used, degradation should becarried out in an extruder to which the components should becontinuously fed. It is understood that the molecular weights of theindividual blend components (e.g., the random copolymer and theisotactic polypropylene) after chain scission are related to the initialmolecular weights of each component. However, each of the componentsundergoes chain scission at separate rates. Accordingly, the molecularweights of the initial components should be adjusted to obtain thedesired molecular weight distribution in the final composition afterchain scission. Also, chain scission of the random copolymer leads tobranching, which is desirable for the adhesive composition.

DETAILED DESCRIPTION

Various specific embodiments, versions and examples of the inventionwill now be described, including preferred embodiments and definitionsthat are adopted herein for purposes of understanding the claimedinvention. It is understood, however, that the scope of the “invention”will refer to the appended claims, including equivalents. All referencesto the “invention” below are intended to distinguish claimedcompositions and methods from compositions and methods not considered tobe part of this invention. It is understood, therefore, that anyreference to the “invention” may refer to one or more, but notnecessarily all, of the inventions defined by the claims.

Polymer Products

Certain embodiments relate to specific types of propylene basedsemicrystalline copolymers, polyolefins that have been largelyoverlooked in adhesive applications. For example, certain propylenebased copolymers having isotactic sequences have lower melt viscositythan ethylene based copolymers and would therefore process better,especially in sprayed adhesive applications. In addition, propylenebased copolymers have higher peak melt points than ethylene basedcopolymers and could therefore be expected to have higher usetemperatures. Finally, certain propylene based copolymers have improvedadhesive strength compared to propylene homopolymers.

One embodiment of the present invention is an adhesive blend preferablycomprising a copolymer of propylene and at least one comonomer selectedfrom the group consisting of ethylene and at least one C₄ to C₂₀α-olefin, preferably having an average propylene content of from atleast about 65 mol % and more preferably from at least about 73 mol %,and most preferably from at least about 85 mol %. Further, the propylenecopolymer has a weight average molecular weight (Mw) preferably fromabout 15,000 to about 200,000 Daltons; more preferably between about50,000 and about 150,000 Daltons; and most preferably between about65,000 and about 100,000 Daltons. Preferably, the propylene copolymer isa semi-crystalline propylene copolymer. The semi-crystalline propylenecopolymer preferably has a melt index (MI) as measured by ASTM D 1238(B)of from about 3000 dg/min to about 7 dg/min, more preferably from about20 dg/min to about 900 dg/min, and most preferably from about 78 toabout 630 dg/min. Additionally, the semi-crystalline propylene copolymercan have a melt index of from about 10 dg/min to about 2500 dg/min, orfrom about 15 dg/min to about 2000 dg/min. The propylene sequences inthe propylene copolymer may be either isotactic propylene sequences orsyndiotactic propylene sequences, preferably isotactic sequences. Thecrystallinity in the propylene copolymer is to be derived from eitherthe isotactic or syndiotactic propylene sequences.

One preferred semicrystalline polymer (SCP) is a thermoplasticcopolymer, preferably random, of ethylene and propylene having a meltingpoint by Differential Scanning Calorimetry (DSC) analysis (ASTME-794-95) of from about 25° C. to about 120° C., preferably in the rangeof from about 30° C. to about 110° C., more preferably in the range offrom about 65° C. to about 100° C. The semi-crystalline polymerpreferably has a weight average molecular weight/number averagemolecular weight ratio (Mw/Mn) of approximately 2. A preferred semicrystalline polymer used in the present invention is described in detailas the “First Polymer Component (SPC)” in co-pending U.S. applicationSer. No. 60/133,966, filed May 13, 1999, which is incorporated byreference herein. The semi-crystalline polymer preferably has a heat offusion from about 30 J/g to about 80 J/g as determined by DSC, morepreferably from about 40 J/g to about 70 J/g as determined by DSC, andmost preferably from about 50 J/g to about 65 J/g as determined by DSC.

A preferred procedure used in the present application for DifferentialScanning Calorimetry (DSC) is described as follows. Preferably, about 6mg to about 10 mg of a sheet of the preferred polymer pressed atapproximately 200° C. to 230° C. is removed with a punch die and isannealed at room temperature for 48 hours. At the end of this period,the sample is placed in a Differential Scanning Calorimeter (PerkinElmer 7 Series Thermal Analysis System) and cooled to about −50° C. to−70° C. The sample is heated at about 10° C./min to attain a finaltemperature of about 180° C. to about 200° C. The thermal output isrecorded as the area under the melting peak of the sample which istypically at a maximum peak at about 30° C. to about 175° C. and occursbetween the temperatures of about 0° C. and about 200° C. The thermaloutput is measured in Joules as a measure of the heat of fusion. Themelting point is recorded as the temperature of the greatest heatabsorption within the range of melting temperature of the sample.

A SCP of the present invention preferably comprises a randomcrystallizable copolymer having a narrow compositional distribution. Theterm “crystallizable,” as used herein for SCP, describes those polymersor sequences which are mainly amorphous in the undeformed state, but cancrystallize upon stretching, annealing or in the presence of anucleating agent, such as a crystalline polymer or a crystalline segmentwithin the polymer. Crystallization is measured by DSC, as describedherein. While not meant to be limited thereby, it is believed that thenarrow composition distribution of the first polymer component isimportant. The intermolecular composition distribution of the polymer isdetermined by thermal fractionation in a solvent. A typical solvent is asaturated hydrocarbon such as hexane or heptane. This thermalfractionation procedure is described in previously mentioned U.S. Ser.No. 60/133,966, incorporated herein by reference. Typically,approximately 75 weight % and more preferably 85 weight % of the polymeris isolated as a one or two adjacent, soluble fraction with the balanceof the polymer in immediately preceding or succeeding fractions. Each ofthese fractions has a composition (mol % ethylene content) with adifference of no greater than 27 mol % (relative) and more preferably 14mol % (relative) of the average mol % ethylene content of the wholefirst polymer component. The first polymer component is narrow incompositional distribution if it meets the fractionation test outlinedabove.

In semi-crystalline polymers, the length and distribution ofstereo-regular propylene sequences is consistent with the substantiallyrandom statistical crystallizable co-polymerization. It is well knownthat sequence length and distribution are related to theco-polymerization reactivity ratios. By substantially random, we meancopolymer for which the product of the reactivity ratios is preferably 2or less, more preferably 1.5 or less, and most preferably 1.2 or less.

In stereo-block structures, the average length of PP sequences isgreater than that in substantially random copolymers with a similarcomposition. Prior art polymers with stereo-block structure have adistribution of PP sequences consistent with these blocky structuresrather than a substantially random statistical distribution. To producea crystallizable copolymer with the required randomness and narrowcomposition distribution, it is desirable to use (1) a single sitedcatalyst and (2) a well-mixed, continuous flow stirred tankpolymerization reactor which allows only a single polymerizationenvironment for substantially all of the polymer chains of the firstpolymer component.

The SCP of the present inventive composition comprises preferablyisotactically crystallizable alpha-olefin sequences, e.g., preferablypropylene sequences (NMR). The crystallinity of the first polymercomponent is, preferably, according to one embodiment, from 1% to 65% ofisotactic polypropylene, preferably between 3% to 30%, as measured bythe heat of fusion of annealed samples of the polymer. The SCPpreferably has a poly dispersity index (PDI) or Mw/Mn between 1.5 to 40,more preferably between about 1.8 to 5 and most preferably between 1.8to 3. Preferably, the SCP has a Mooney viscosity of ML (1+4)@125° C.less than 40, more preferably less than 20 and most preferably less than10. It is preferred that the SCP has a melt index (MI) at 190° C. ofless than about 1500 dg/min, more preferably less than about 900 dg/min,and most preferably less than 650 dg/min. Further, the semi-crystallinepropylene copolymer can also have a melt index of from about 10 dg/minto about 2500 dg/min, or from about 15 dg/min to about 2000 dg/min, oreven more broadly from about 7 dg/min to about 3000 dg/min.

The low levels of crystallinity in the SCP are obtained by incorporatingfrom about 0.5 to 50 mol % alpha-olefin, preferably from about 0.9 toabout 35 mol % alpha-olefin; more preferably, it comprises from about1.3 to about 37 mol % alpha-olefin, and; most preferably between about1.3 to about 15 mol % alpha-olefin. Alpha olefins are defined herein tocomprise one or more members of the group consisting of ethylene andC₄-C₂₀ alpha-olefin. At alpha-olefin compositions lower than the abovelower limits for the composition of the SCP, the blends of the SCP arethermoplastic. At alpha-olefin compositions within the stated desiredranges, the blends exhibit superior tensile strength. At alpha-olefincompositions higher than the above higher limits for the SCP, the blendshave poor tensile strength. It is believed, while not meant to belimited thereby, the SCP needs to have the optimum amount of isotacticpolypropylene crystallinity to crystallize for the beneficial effects ofthe present invention. As discussed above, the most preferred co-monomeris ethylene.

Preferably, the adhesive blend further comprises one or more additives,such as tackifiers, plasticizers (extender oils), waxes, colorants,antioxidants, fillers and others conventionally used in adhesive blends.More preferably, the adhesive composition comprises from 0 to about 80weight percent of at least one tackifier; from 0 to about 60 weightpercent of at least one plasticizer; and from 0 to about 50 weightpercent of at least one wax; from 0 to about 5 weight percent of ananti-oxidant, wherein the sum of the components (b), (c), and (d)comprises from about 5 to about 95 weight percent of said adhesivecomposition.

Suitable plasticizers or extender oils include aromatic, naphthenic,paraffinic, or hydrogenated (white) oils and mixtures thereof. One ofthe particular advantages of the invention is that none or only minoramounts of extender oil may be required to achieve good flow and coatingcharacteristics because of the inherently low melt viscosity propertiesof the adhesive of the invention. Reduction in the level of extender oilrequired to process the composition tends to result in improvedcohesiveness of the adhesive and reduces bleed out of the extender.Where used, the extender oil is added at a level from about 0.5 to about25 parts by weight per hundred parts by weight of the SCP, morepreferably from about 5 to 15 parts by weight.

Suitable antioxidants include hindered phenols such as2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)-benzene;tetrakis [(methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane(IRGANOX™ 1010, commercially available from Ciba Geigy, New York);octadecyl-3,5-di-t-butyl-4-hydroxy cinnamate (IRGANOX™ 1076,commercially available from Ciba Geigy); and like known materials. Wherepresent, the antioxidant is used at a preferred level of from about 0.05to about 2 parts by weight per 100 parts by weight of composition. Thestabilizing additives, antioxidants, and/or UV stabilizers used inaccordance with the invention, are well known conventionally anddescribed in the literature, see for example, U.S. Pat. No. 5,143,968and U.S. Pat. No. 5,656,698. These patents are expressly incorporated byreference for their teachings as to antioxidant stabilizers andplasticizer oils.

The primary tackifying resins useful in the practice of this inventionpreferably include hydrocarbon resins, synthetic polyterpenes, rosin,rosin esters and natural terpenes which are solids, semi-solids, orliquids at room temperature. The various types of resins are describedin U.S. Pat. No. 5,143,968, incorporated herein by reference. Thepreferred tackifying resins are aliphatic hydrocarbon resins such as (1)resins resulting from the polymerization of monomers consisting ofolefins and diolefins (e.g., Escorez® 1310LC, Escorez® 2596 ofExxonMobil Chemical Company, Houston, Tex.) and the hydrogenated versionthereof, alicyclic petroleum hydrocarbon resins and the hydrogenatedderivatives (e.g. Escorez® 5300 and 5400 series from ExxonMobilChemical; Eastotac® resins from Eastman Chemical, Kingsport, Tenn.); (3)polyterpene resins and hydrogenated derivatives; (4) hydrogenated C9(e.g., Arkon® P series from Arakawa Chemical; Regalrez® and Regalite R®from Hercules, Wilmington, Del.). The tackifier resins may also bemodified with some aromatic components, such as Escorez® 2596commercially available from ExxonMobil Chemical Co., the level of whichshould not be too high to cause incompatibility with the SCP of thisinvention. The hot melt adhesive compositions of the inventionpreferably will contain from about 20 to about 70 wt. %, more preferablyfrom about 35 to about 60 wt. % tackifying resin.

The wax component of the invention adhesive compositions will be any ofthose conventionally known for use with EVA in hot melt adhesivecompositions. Exemplary petroleum derived synthetic waxes are paraffinand microcrystalline waxes having melting points within a range of fromabout 55° C. to about 110° C. as well as low molecular weightpolyethylene and Fischer-Tropsch waxes. The wax content is preferablyfrom about 10 to about 35 wt. % of the total blend composition.Plasticizers, pigments and fillers may be used along with or in place ofa portion of the wax. Plasticizer oils can be used, see U.S. Pat. No.5,143,968, incorporated herein by reference, for description of suitableoils.

As indicated above, the components forming the adhesive formulations ofthe invention have properties such that adhesives having a very low meltviscosity are provided, thereby facilitating flow of the adhesivethrough the coating apparatus, e.g., coating die, without resorting tothe inclusion of solvents or excess extender oil into the composition.Melt viscosities of less than 10,000 centipoise measured at 180° C. perASTM D 3236 can be readily achieved for the adhesive blend. The morepreferred melt viscosity at 180° C. is less than 2,000 cps and the mostpreferred melt viscosity at 180° C. is approximately 1500 cps.

Typical industrial applications include packaging, particularly for lowtemperature use such as for dairy products or for freezer packaging offood products, and in sanitary disposable consumer articles, forexample, diapers, feminine care pads, napkins, etc. However, even moretraditional end use applications such as book-binding, wood working andlabeling will also benefit from both the low temperature flexibility,heat resistance and the efficiency of end use in automated means ofapplying the invention compositions to the various art-recognizedsubstrates or adherends. In a preferred embodiment, the adhesivecompositions of the present invention are hot melt adhesives. In anotherembodiment, other polyolefins, preferably isotactic polypropylenes, suchas Achieve™3866G, commercially available from ExxonMobil Chemical Co.,Baytown, Tex., can be used as blend components in the adhesivecomposition of the present invention.

The hot melt adhesive compositions may be applied to the desiredsubstrate or adhered in any manner known in the art, particularly thosemethods used traditionally for packaging. Typically a coating head ornozzle, with associated equipment, for example those manufactured byNordson Corporation, Duluth, Ga., are used. The compositions can beapplied as fine lines, dots or spray coatings, in addition to othertraditional forms as desired.

Catalysts

Suitable catalysts include bis metallocene complexes with the same ordifferent cyclopentadienyl ligands capable of producing stereoregularpropylene sequences (either isotactic or syndiotactic, preferablyisotactic). The preferred metallocenes are those that are chiral andstereorigid so as to impart isotactic polypropylene sequences, which arewell known to one skilled in the art

Preferred transition metal compound components are described in detailin U.S. Pat. Nos. 5,145,819; 5,243,001; 5,239,022; 5,329,033; 5,296,434;5,276,208; 5,672,668, 5,304,614 and 5,374,752; and EP 549 900 and 576970 all of which are herein fully incorporated by reference.

Selection of metallocene compounds for use to make isotactic orsyndiotactic polypropylene, and their syntheses, are well-known in theart, specific reference may be made to both patent literature andacademic, see for example Journal of Organometallic Chemistry 369,359-370 (1989). Typically those catalysts are stereorigid asymmetric,chiral or bridged chiral metallocenes. Either the rac- or meso-isomerscan be used. Catalyst selection should lead to the same type oftacticity for each of the propylene-based polymer compounds. Preferredcatalysts lead to isotactic polymers. See, for example, U.S. Pat. No.4,892,851, U.S. Pat. No. 5,017,714, U.S. Pat. No. 5,296,434, U.S. Pat.No. 5,278,264, WO-A-(PCT/US92/10066) WO-A-93/19103, EP-A2-0 577 581,EP-A1-0 578 838, and academic literature “The Influence of AromaticSubstituents on the Polymerization Behavior of Bridged ZirconoceneCatalysts”, Spaleck, W., et al, Organometallics 1994, 13, 954-963, and“ansa-Zirconocene Polymerization Catalysts with Annelated RingLigands-Effects on Catalytic Activity and Polymer Chain Lengths”,Brinzinger, H., et al, Organometallics 1994, 13, 964-970, and documentsreferred to therein.

Additional bridged metallocene compounds, particularly preferred forstereoregular copolymer catalysis include:

-   Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zirconium dimethyl-   Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zirconium dimethyl;-   Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zirconium    dimethyl;-   Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zirconium dimethyl;-   Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zirconium    dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2-methyl-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zirconium dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconium    dimethyl,-   1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconium    dimethyl,-   1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl)Zirconium    dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2,4-dimethyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-α-acenaphth-1-indenyl)Zirconium    dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium    dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zirconium    dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zirconium    dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-a-acenaphth-1-indenyl)Zirconium    dimethyl,-   1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium dimethyl,-   1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium    dimethyl,-   1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-1-indenyl)Zirconium dimethyl,-   1,2-Ethandiylbis(2-methyl-1-indenyl)Zirconium dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-1-indenyl)Zirconium dimethyl,-   Diphenylsilandiylbis(2-methyl-1-indenyl)Zirconium dimethyl,-   1,2-Butandiylbis(2-methyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-ethyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)Zirconium    dimethyl,-   Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl)Zirconium    dimethyl,-   Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zirconium dimethyl,-   Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zirconium    dichloride-   Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zirconium dichloride,-   Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zirconium    dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-indenyl)Zirconium dichloride,-   Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zirconium dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconium    dichloride,-   1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconium    dichloride,-   1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl)Zirconium    dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2,4-dimethyl-1-indenyl)Zirconium dichloride,-   Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-α-acenaphth-1-indenyl)Zirconium    dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium    dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zirconium    dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)    Zirconium dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-a-acenaphth-1-indenyl)Zirconium    dichloride,-   1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium dichloride,-   1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium dichloride,-   Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl)Zirconium    dichloride,-   1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)Zirconium dichloride,-   Dimethylsilandiylbis(2-methyl-1-indenyl)Zirconium dichloride,-   1,2-Ethandiylbis(2-methyl-1-indenyl)Zirconium dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-1-indenyl)Zirconium dichloride,-   Diphenylsilandiylbis(2-methyl-1-indenyl)Zirconium dichloride,-   1,2-Butandiylbis(2-methyl-1-indenyl)Zirconium dichloride,-   Dimethylsilandiylbis(2-ethyl-1-indenyl)Zirconium dichloride,-   Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)Zirconium    dichloride,-   Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl)Zirconium    dichloride,-   Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zirconium dichloride,    and the like, particularly the structurally similar hafnium    compounds.

Additionally, metallocenes such as those described in U.S. Pat. No.5,510,502, U.S. Pat. No. 4,931,417, U.S. Pat. No. 5,532,396, U.S. Pat.No. 5,543,373, WO 98/014585, EP611 773 and WO 98/22486 (each fullyincorporated herein by reference) are suitable for use in thisinvention.

Co-Catalysts

For the purposes of this patent specification and appended claims, theterms “cocatalysts” and “activators” are used interchangeably and aredefined to be any compound or component which can activate a metallocenecompound, as defined above. For example, a Lewis acid, anon-coordinating ionic activator, an ionizing activator, or any othercompound that can convert a metallocene catalyst precursor to acatalytically active metallocene cation is an activator or cocatalyst.

It is within the scope of this invention to use, as an activator for oneor more metallocenes, alumoxane and/or to also use ionizing activators,neutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate, dimethyl aniliniumtetrakis(pentafluorophenyl) borate, trityl tetrakis(pentafluorophenyl)borate, or a trisperfluorophenyl boron metalloid precursor which ionizethe neutral metallocene compound. Dimethylaniliniumtetrakis(pentafluorophenyl)borate is a particularly preferred activatorfor the above named metallocenes. Generally, fluoroaryl boron andaluminum compounds as neutral Lewis acids or as ionic salts comprisingcations capable of protonating or abstracting an alkyl metalloceneligand will be suitable. Additional non-coordinating anions that may beuseful in the present application may include but are not limited tothose disclosed in U.S. Pat. Nos. 5,198,401, 5,296,433, 5,278,119,5,407,884, EP 0 426 637, EP 0 500 944, EP 0 520 732, WO 95/24268, and WO97/29845.

The metallocene can be used with a cocatalyst which may be alumoxanepreferably methylalumoxane having an average degree of oligomerizationof from 4 to 30 as determined by vapor pressure osmometry. Alumoxane maybe modified to provide solubility in linear alkanes but is generallyused from a toluene solution. Such solutions may include unreactedtrialkylaluminum and the alumoxane concentration is generally indicatedon Mol Al per liter, which figure includes any trialkyl aluminum whichhas not reacted to form an oligomer. The alumoxane, when used ascocatalyst, is generally used in molar excess, at a mol ratio of from 50to 1000, preferably from about 100 to about 500.

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529 and EP-A-0 561476, EP-B1-0 279 586, EP-A-0 594-218 and WO 94/10180, all of which arefully incorporated herein by reference.

Scavengers

When using the catalysts of the invention, the total catalyst systemwill generally additionally comprise one or more organometalliccompound. Such compounds as used in this application is meant to includethose compounds effective for removing polar impurities from thereaction environment and for increasing catalyst activity. Impuritiescan be inadvertently introduced with any of the polymerization reactioncomponents, particularly with solvent, monomer and catalyst feed, andadversely affect catalyst activity and stability. It can result indecreasing or even elimination of catalytic activity, particularly whenionizing anion pre-cursors activate the catalyst system. The polarimpurities, or catalyst poisons include water, oxygen, metal impurities,etc. Preferably steps are taken before provision of such into thereaction vessel, for example by chemical treatment or careful separationtechniques after or during the synthesis or preparation of the variouscomponents, but some minor amounts of organometallic compound will stillnormally be used in the polymerization process itself.

Typically these compounds will be organometallic compounds such as theGroup-13 organometallic compounds of U.S. Pat. Nos. 5,153,157, 5,241,025and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132, and that of WO95/07941. Exemplary compounds include triethyl aluminum, triethylborane, triisobutyl aluminum, methylalumoxane, and isobutylaluminumoxane. Those compounds having bulky or C₆-C₂₀ linear hydrocarbylsubstituents covalently bound to the metal or metalloid center beingpreferred to minimize adverse interaction with the active catalyst.Examples include triethylaluminum, but more preferably, bulky compoundssuch as triisobutylaluminum, triisoprenylaluminum, and long-chain linearalkyl-substituted aluminum compounds, such as tri-n-hexylaluminum,tri-n-octylaluminum, or tri-n-dodecylaluminum. When alumoxane is used asactivator, any excess over the amount needed to activate the catalystspresent can act as a poison scavenger compound and additionalorganometallic compounds may not be necessary. Alumoxanes also may beused in scavenging amounts with other means of activation, e.g.,methylalumoxane and triisobutyl-aluminoxane with aryl boron or arylaluminum activators. The amount of such compounds to be used withcatalyst compounds of the inventions is minimized during polymerizationreactions to that amount effective to enhance activity (and with thatamount necessary for activation of the catalyst compounds If used in adual role) since excess amounts may act as catalyst poisons.

Solvents

Aliphatic, cycloalphatic, and aromatic hydrocarbons may be used assolvents during the polymerization process. Preferred solvents are C₁₂or lower straight-chain or branched-chain, saturated hydrocarbons, andC₅ to C₉ saturated alicyclic or aromatic hydrocarbons. Examples of suchsolvents or reaction media are hexanes, butane, pentane, heptane,cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylene and mixtures thereof.In addition, one or more-olefins, either alone or admixed with othermedia, may serve as the reaction media, at selected concentrations ofsuch olefins. A mixture of hexanes is most preferred.

Polymerization Processes

A typical polymerization process consists of a polymerization in thepresence of a catalyst comprising a chiral metal compound and either 1)a non-coordinating compatible anion activator, or 2) an alumoxaneactivator. According to one embodiment of the invention, this comprisesthe steps of contacting ethylene and propylene with a catalyst in asuitable polymerization diluent, said catalyst comprising, for example,according to a preferred embodiment, a chiral metallocene catalyst,e.g., a bis(cyclopentadienyl) metal compound, and an activator. As notedabove, the activator used may be an alumoxane activator or anon-coordination compatible anion activator. The alumoxane activator ispreferably utilized in an amount to provide a molar aluminum tometallocene ratio of from about 1:1 to about 20,000:1 or more. Thenon-coordinating compatible anion activator is preferably utilized in anamount to provide a molar ratio of biscyclopentadienyl metal compound tonon-coordinating anion of 10:1 to about 1:1. The above polymerizationreaction is conducted by reacting such monomers in the presence of suchcatalyst system at a temperature of from about −100° C. to about 300° C.for a time of from about 1 second to about 10 hours to produce acopolymer having a weight average molecular weight of from about 5,000or less to about 1,000,000 or more and a molecular weight distributionof from about 1.8 to about 4.5.

While the process of the present invention includes utilizing a catalystsystem in the liquid phase (slurry, solution, suspension or bulk phaseor combination thereof), according to other embodiments, high-pressurefluid phase or gas phase polymerization may also be utilized. Whenutilized in a gas phase, slurry phase or suspension phasepolymerization, the catalyst systems will preferably be supportedcatalyst systems. See, for example, U.S. Pat. Nos. 5,057,475 and5,643,847, incorporated herein by reference for purposes of U.S.practice. Such catalyst systems can also include other well-knownadditives such as, for example, scavengers. See, for example, U.S. Pat.No. 5,153,157, which is incorporated herein by reference for purposes ofU.S. practices. These processes may be employed without limitation ofthe type of reaction vessels.

As stated above, and while it is also true for systems utilizing asupported catalyst system, the liquid phase process comprises the stepsof contacting ethylene and propylene with the catalyst system in asuitable polymerization diluent and reacting the monomers in thepresence of the catalyst system for a time and at a temperaturesufficient to produce an ethylene-propylene copolymer of the desiredmolecular weight and composition.

According to one embodiment of the invention, the polymerization processcomprises (a) reacting by contacting of propylene and at least onecomonomer selected from the group consisting of ethylene and at leastone C₄ to C₂₀ α-olefin, under suitable polymerization conditions,preferably solution polymerization conditions, in the presence of asuitable catalyst, such as metallocene, in at least one first reactor.The metallocene catalyst must be capable of incorporating the propylenesequences into isotactic or syndiotactic orientations. Suitablepolymerization conditions are more fully exemplified in the followingexamples. A preferred solvent is hexane. The polymerization produces acopolymer having greater than 65 mol % propylene wherein at least aportion, preferably 40 mol %, of the propylene sequences are inisotactic or syndiotactic orientations.

Further, one may (b) optionally, in at least a second or subsequentreactors, polymerize of propylene and at least one comonomer selectedfrom the group consisting of ethylene and at least one C₄ to C₂₀α-olefin, under suitable polymerization conditions, preferably solutionpolymerization conditions, in the presence of a metallocene catalyst.Although the solvent and monomers can be fed to each reactor, preferablythe catalyst is fed to the first reactor only. The polymerization in thesecond reactor may duplicate the polymerization in the first reactor,that is, produce a copolymer that is approximately greater than 65 mol %propylene wherein at least a portion, preferably 40 mol % of thepropylene sequences are in isotactic or syndiotactic orientations.

The solutions of the first reactor preferably are combined with thesolutions of the subsequent reactors to form a solution containing ablend of polymers. The solvent is then preferably removed from thesolution of the blend and the blend is recovered, and optionally, atackifier may be added into the first reactor of step (a), the second orsubsequent reactors of step (b), or at any point subsequent to thereactor in step (b).

Series reactor or parallel reactor operation can be used to increase thecrystallinity without increasing the brittleness of the adhesive bymaking copolymers with higher propylene content in one reactor (and thushaving a higher melt temperature which provides a higher usetemperature) and then making a copolymer with lower propylene content inthe other reactor (and thus being more amorphous which provides greatertack, softness, and better low temperature properties). Combined theymake a better hot melt adhesive.

In general, the propylene based copolymers of the present inventionpreferably have a narrow molecular weight distribution for single sitedmetallocene catalyst products. However, the blends resulting from seriesor parallel reactor operations as described herein provide tailoredmolecular weight distributions by choosing suitable conditions, as willbe described in detail in the following examples, such that differentmolecular weight polymers are made in each reactor, resulting in bimodalor multimodal blends.

Reactor Operations (General)

One or more stirred tank reactors in series or in parallel may be usedin the present invention. The reactor operation is a solutioncopolymerization using the suitable described catalysts. Catalyst andactivator may be delivered as a solution or slurry, either separately tothe reactor (in-situ), activated in-line just prior to the reactor, orpreactivated and pumped as an activated solution or slurry to thereactor. The preferred operation is two solutions activated in-line.

Polymerizations are carried out in either single reactor operation, inwhich solvent, monomer, comonomers, catalyst/activator, scavenger, andoptional modifiers are added continuously to a single stirred tank or inseries reactor operation, in which the above components (except for thecatalyst) are added to each of two or more reactors connected in seriesand said monomers are allowed to react for a sufficient time to producethe invention copolymers. The catalyst component must be added to thefirst reactor in the series. The catalyst component may also be added toboth reactors, but preferably, is added only to the first reactor.

Generally speaking the polymerization reaction temperature can vary fromabout 40° C. to about 250° C. Preferably the polymerization reactiontemperature will be from 60° C. to 220° C. The pressure can vary fromabout 1 mm Hg to 2500 bar, preferably from 0.1 bar to 1600 bar, mostpreferably from 1.0 to 500 bar.

The process can be carried out in a continuous stirred tank reactor, ormore than one operated in series or parallel. These reactors may have ormay not have internal cooling and the monomer feed my or may not berefrigerated. See the general disclosure of U.S. Pat. No. 5,001,205 forgeneral process conditions. See also, international application WO96/33227 and WO 97/22639. All documents are incorporated by referencefor description of polymerization processes, metallocene selection anduseful scavenging compounds.

In one preferred process, all feeds are pumped into the reactors bymetering pumps except for the ethylene (and hydrogen where applicable)which flow as a gas under its own pressure through a mass flowmeter/controller. In an alternative process, monomer may be added to thereactor by a preformed solution. The polymer composition may becontrolled by adjustment of the ethylene head pressure over the feedsolution.

Temperature control in the reactor is obtained by balancing the heat ofpolymerization and with reactor cooling by reactor jackets or coolingcoils to cool the contents of the reactor, auto refrigeration,prechilled feeds or combinations of all three. Adiabatic reactors withprechilled feeds are preferred. The reactor temperature depends on thecatalyst used. In general, the reactor temperature preferably can varybetween about 0° C. and about 160° C., more preferably from about 10° C.to about 140° C., and most preferably from about 40° C. to about 120° C.In series operation, the second reactor temperature is preferably higherthan the first reactor temperature. In parallel reactor operation, thetemperatures of the two reactors are independent.

The polymer composition is preferably controlled by the amount ofmonomers fed to each reactor of the series. In a single reactor series,unreacted monomers are flashed off in the polymer workup. In a tworeactor series, unreacted monomers from the first reactor flow into thesecond reactor and so the monomers added to the second reactor are justenough to adjust the composition of the feed to the desired level,taking into account the monomer carry over.

The molecular weight of the polymer is controlled by the reactortemperature and by the addition of chain transfer agents such ashydrogen. With metallocene catalysts, polymer molecular weight generallydeclines with increasing reaction temperature and increasing transferagents. In a two reactor series for adiabatic reactor operation with ahigher temperature in the second reactor, it is easier to make the lowmolecular weight component in the second reactor. Molecular weight inthe second reactor can be further reduced and the molecular weightdistribution (MWD) of the subsequent blend may be broadened by addinghydrogen to the second reactor. Hydrogen can also be added to the firstreactor but because unreacted hydrogen will carry over to the secondreactor the molecular weight of both polymer components will bedecreased in this situation and the effect of hydrogen on MWD will bemuch less. In parallel reactor operation the monomer, comonomer,catalyst, hydrogen, scavenger, solvent and other feeds are all treatedindependently.

Single Reactor Polymerization Processes

Polymerizations are carried out in a single, stirred reactor withcontinuous flow of feeds to the system and continuous withdrawal ofproducts. In certain examples a one-liter stirred reactor was used.Solvent, including but not limited to hexane, and monomers including butnot limited to, propylene and ethylene are preferably purified usingfiltering membranes or mechanical devices, preferably beds of aluminaand mole sieves. The solvent for preparing catalyst solutions may alsobe purified by the same technique.

The reactor temperature is preferably controlled by circulatingsteam/water through a reactor jacket. The reactors are maintained at apressure in excess of the vapor pressure of the reactant mixture to keepthe reactants in the liquid phase. The reactors are operated liquidfull. Propylene and ethylene feeds are mixed with a hexane stream thathas been cooled, preferably from about 0° C. to about −50° C.Alternatively, if ENB (ethylidene norbornene) is used, it is also fedinto the hexane stream upstream of the other monomers. A hexane solutionof triisobutyl aluminum scavenger is added to the combined solvent andmonomer stream preferably just before it enters the reactor to furtherreduce the concentration of any catalyst poisons. The catalystcomponents in the solvent, preferably toluene or toluene/hexanemixtures, are either preactivated in one solution and pumped together ordissolved as two single component solutions and pumped separately to thereactor. Preferably, in most cases, the catalyst is activated in-linejust prior to the reactor. The activated catalyst enters the reactorthrough a separate port outfitted with a dip tube to ensure adequatedistribution. The polymer/solvent/unconverted monomers, and catalystsolution exit the reactor through a pressure control valve that reducesthe pressure of the polymerization process to atmospheric pressure. Thereduction to atmospheric pressure causes the unconverted monomers in thesolution to flash into a vapor phase that is preferably vented from thetop of a vapor-liquid separator. The liquid phase, including, for themost part, polymer and solvent, flows out the bottom of the separatorand is collected for polymer recovery. After removing a small portion ofthe polymer for determining polymer concentration, a stabilizer ispreferably added to the polymer solution. The stabilized polymer isrecovered from the solution by either steam stripping, followed byvacuum drying, or by solvent evaporation over heat and vacuum drying.

Gel Permeation Chromatography (GPC) techniques that were used tocharacterize the products of this invention have been described inseveral publications notably U.S. Pat. No. 4,989,436 which isincorporated for purposes of U.S. patent practice. Molecular weight andcomposition measurements are described in G. Ver Strate, C. Cozewith, S.Ju, Macromolecules, 21, 3360 (1988) which is incorporated by referencefor purposes of U.S. patent practice. The variety of other techniquesused are soundly based in polymer structure characterization asdescribed in “Structure Characterization” The Science and Technology ofElastomers, F. Eirich, editor, Academic Press 1978 Chapter 3 by G. VerStrate.

The glass transition temperature Tg (ASTM E-1356-95), the melttemperature Tm (ASTM E-794-95), and heat of fusion (ASTM E-793-95) andcrystallization are evaluated based on the measurements from the firstmelt and the quench. In some cases, low melting crystallinity will notbe seen on the second scan as it may take many hours to develop even atlow temperatures.

Samples of the polymer solution from the reactor were analyzed forpolymer concentration. From this measurement and the reactor feed ratesthe polymerization rate (referred to as Poly Rate herein) could bedetermined by material balances. Monomer conversions were thencalculated from the polymerization rate and polymer composition data.

Reactor conditions and feed rates are shown in Table 1. Table 2 comparesthe polymer properties and Table 3 compares the formulated adhesivecompositions.

High MFR Adhesives

Certain embodiments of the invention involve high MFR adhesives,specifically, adhesive compositions that include a polymer or blend ofpolymers having an MFR greater than 250 dg/min of 230° C. The followingdiscussion relates to the high MFR adhesive compositions, particularlythose discussed below. However, certain specific embodiments of theinvention include treating any one of the polymers or polymer blendsdescribed above with a free radical initiator, e.g., peroxide, to obtainan adhesive composition with an MFR greater than 250 dg/min.

A specific embodiment of this invention is directed to adhesivecompositions having an MFR greater than about 250 dg/min. at 230° C.,the composition including a random copolymer produced by copolymerizingpropylene and at least one of ethylene or an alpha-olefin having 3 to 8carbon atoms, the random copolymer having a crystallinity at least about2% and no greater than about 65% derived from stereoregularpolypropylene sequences and a melting point of from about 25° C. toabout 105° C. It is understood that while the overall composition mayinclude additional ingredients that may further increase the overall MFRof the composition, it is the MFR of the polymer or blend of polymersthat is referred to herein, e.g., following treatment with a peroxide orother free radical initiator, which results in modification of the MFRof the polymer. Advantageously, therefore, additional treatment steps orMFR-increasing additives are not necessarily required. In a specificembodiment, the polymers having the high MFR are mixed with otheradditives, discussed below, and can be used directly as an adhesive,e.g., in sprayable form. The adhesives can be used in any number ofmanufactured articles, including those discussed above. Preferably, theadhesive compositions discussed herein, having a polymer or blend ofpolymers with high MFR are used in conventional “hot melt adhesive”applications.

Another specific embodiment is directed to an adhesive compositionincluding the reaction product of a free radical initiator and a randomcopolymer produced by copolymerizing propylene and at least one ofethylene or an alpha-olefin having 20 or less carbon atoms, preferably 8or less carbon atoms, the random copolymer having a crystallinity atleast about 2% and no greater than about 65% derived from stereoregularpolypropylene sequences and a melting point of from about 25° C. toabout 105° C. Preferably, the reaction product, a modified polymer, hasan MFR 250 or greater as discussed in greater detail elsewhere herein.

Any of the high MFR adhesives compositions described herein mayadditionally include any one or more of the additives discussed above,such as tackifiers, plasticizers (e.g., extender oils), waxes,colorants, antioxidants and other fillers that are conventionally usedin adhesive compositions.

Another specific embodiment of the invention includes an adhesivecomposition formed by treating a polymer composition in the melted statewith a free-radical initiator in an amount effective to increase the MFRat 230° C. by at least 100% Preferably, the copolymer is the product ofa single step polymerization process and is an ethylene/propylenecopolymer.

The free-radical initiator, e.g., peroxide, may be added to the polymerwhile the polymer is in a solid form, e.g., by coating polymer pelletswith an initiator, such as peroxide, which may be in powder form, inwhich case the polymer is said to be “treated” with the initiator whenthe initiator becomes active, which usually happens at a temperaturehigher than melting point of the polymer. Preferably, however, thefree-radical initiator is added to the polymer after the polymer hasformed, but while the polymer is in a melted condition, e.g., during thepost-polymerization processing, such as when a polymer mixture (whichmay include solvent) is introduced to a devolatalizer or extruder, whichtypically occurs at an elevated temperature. The term “melted” refers tothe condition of the polymer when any portion of the polymer is melted,and includes both fully melted and partially melted. Preferably, thepolymer is treated by the free-radical initiator while the temperatureof the polymer is above its melting point.

In another specific embodiment, the free radical initiator used in anadhesive composition disclosed herein includes a peroxide. As but oneexample, the peroxide may be2,5-bis(tert-butylperoxy)-2,5-dimethyl-hexane. Any other peroxide thatpromotes free radicals are also included within the definition of“peroxide.” Alternatively, the free radical initiator may include adiazo compound, or any other compound that promotes free radicals in anamount sufficient to cause degradation as specified herein.

In a specific embodiment an adhesive composition identified above may besimultaneously degraded through chain scission and crosslinked, whereinthe extent of degradation through chain scission is greater than theextent of crosslinking. This is preferably accomplished by limiting theethylene content in the polymer or polymer blend. It is recognized bythe inventors that too much ethylene (or alpha olefin) causes thecrosslinking to predominate, thus preventing chain scission anddegradation. However, there is preferably sufficient ethylene to providea melting point between 80 and 100 degrees C. Preferably, the ethyleneor alpha olefin content is maintained below about 39 mole %.

Broadly, the adhesive compositions herein may have a molecular weightdistribution between about 1.8 and 5.0. More narrowly, the adhesivecompositions above may have a molecular weight distribution betweenabout 2.0 and 3.2.

Preferably, the adhesive compositions herein may include ethylene oralpha-olefin with a narrow composition distribution. In a more specificembodiment, the composition distribution may be no greater than about 14mole %. In any of the adhesive compositions above, the random copolymermay be produced by copolymerizing propylene and ethylene, wherein thecomposition distribution of ethylene is no greater than about 27 mole %.

In any of the adhesive compositions herein, the random copolymer may bea branched random copolymer. In a specific embodiment, more than about50% of the molecules of the random copolymer may be branched molecules.In a more specific embodiment, more than about 80% of the molecules ofthe random copolymer may be branched molecules.

In a specific embodiment of the adhesive composition, the randomcopolymer includes from at least about 6 mole % to no greater than about33 mole % ethylene units or alpha-olefin units having 8 or less carbonatoms.

In another specific embodiment, the random copolymer of the adhesivecomposition may include more than about 67 mole % by weight propyleneunits (e.g., C3/C2). More specifically, the random copolymer of theadhesive composition may include more than about 80% by weight propyleneunits.

In a specific embodiment, although the adhesive composition may have anMFR greater than about 250 dg/min. at 230° C., it may also have an MFRof at least about 350 dg/min. at 230° C. More narrowly, the adhesivecomposition may have an MFR of at least about 500 dg/min. at 230° C. Ina specific embodiment of any of the adhesive compositions identifiedabove, the free radical initiator used to form the reaction product maybe in the amount of at least about 0.25 wt % and no greater than about5.00 wt %, based on the weight of the random copolymer.

In yet another specific embodiment, the adhesive composition may includea polymer or polymer blend, e.g., a semi-crystalline propylene copolymersuch as those described herein, with a melt index (MI) as measured byASTM D 1238(B) of from about 3000 dg/min to about 7 dg/min, or fromabout 2500 to about 10 dg/min, or from about 2000 to about 15 dg/min, orfrom about 900 to about 20 dg/min, or from about 78 to about 630 dg/min.Preferably, the polymer or polymer or polymer blend has the abovedescribed MI ranges, either following formation of the polymer in apolymerization reaction as discussed above, or following degradationtreatment, and preferably has those MI values without additionalprocessing or use of additives.

For example, the free radical initiator used to form the reactionproduct may be in the amount of at least about 0.50 wt % and no greaterthan about 3.00 wt %, based on the weight of the random copolymer.

Alternatively, the free radical initiator used to form the reactionproduct may be in the amount of at least about 1.00 wt % and no greaterthan about 2.00 wt %, based on the weight of the random copolymer. Theranges of the amounts of free radical initiators may fall between any ofthe amounts identified any of the Examples below, e.g., between 0.33 wt% and 1.00 wt %.

Preferably, the adhesive composition of this invention is a blend thatincludes a crystalline polymer blended with the random copolymer. Morespecifically, the adhesive composition may be a blend that includes acrystalline polymer blended with the random copolymer, wherein thecrystalline polymer has a melting point greater than at least about 110NC. More narrowly, the crystalline polymer may have a melting pointgreater than about 115 NC. More specifically, the crystalline polymermay have a melting point greater than about 130° C.

In a specific embodiment, any of the adhesive compositions mentionedherein may be or include a blend that includes a crystalline polymerblended with the random copolymer, wherein the crystalline polymerincludes polypropylene or a copolymer comprising propylene units and atleast one comonomer selected from the group consisting of ethylene orC4-C 12 alpha-olefins, the copolymer having a comonomer content of lessthan about 14 mole %.

In a specific version of the disclosed adhesive compositions, thecomonomer content may range up to about 12 mole %. Preferably, thecomonomer content may range from about 7 mole % to about 12 mole %. In aspecific embodiment, the comonomer content is less than about 3 mole %.

In another specific embodiment, the propylene content of the randomcopolymers of any of the disclosed adhesive compositions may be betweenabout 55 mole % or greater and about 93 mole % or less. Morespecifically, the propylene content of the random copolymer may be about60 mole % or greater. More narrowly still, the propylene content of therandom copolymer may be about 73 mole % or greater. Also, the upperlimit of the random copolymer may be lower than 93 mole %. For example,in specific embodiments of this invention, the propylene content of therandom copolymer is about 89 mole % or less. Alternatively, thepropylene content of the random copolymer may be about 85 mole % orless. Additionally, the propylene content of the random copolymer may beabout 84 mole % or less.

The crystalline polymer of any of the adhesive compositions identifiedherein may include isotactic polypropylene. The isotactic polypropylenemay have a melting point greater than 110° C. Alternatively, theisotactic polypropylene may have a melting point greater than 115° C.More specifically, the isotactic polypropylene may have a melting pointgreater than 130° C.

As mentioned above, another aspect of this invention is directed to aprocess. A specific embodiment of this invention involves a process formaking a degraded adhesive composition, including: (a) providing a firstpolymer composition having an MFR less than 250 dg/min. at 230° C. andcomprising a random copolymer produced by copolymerizing propylene andat least one of ethylene or alpha-olefin having 4 to 20 carbon atoms,preferably 4 to 8 carbon atoms, the random copolymer having acrystallinity at least about 2% and no greater than about 65% derivedfrom stereoregular polypropylene sequences and a melting point of fromabout 25° C. to about 105° C.; and (b) contacting the first polymercomposition, in the melted state, with a free radical initiator, toprovide a second polymer composition, where the second polymercomposition has an MFR greater than 250 dg/min. at 230° C.

In any degradation process identified elsewhere herein, the firstpolymer composition may have an MFR less than 50 dg/min. at 230° C.prior to contacting the first polymer composition with the free radicalinitiator. In a specific embodiment of the process, the free radicalinitiator may include a peroxide. Specifically, the free radicalinitiator may include 2,5-bis(tert-butylperoxy)-2,5-dimethyl-hexane.Alternatively, the free radical initiator may include a diazo compound.

In any of the degradation processes disclosed herein, the first polymercomposition may be both degraded through chain scission and crosslinkedin the presence of the free radical initiator, wherein the extent ofdegradation through chain scission should be greater than the extent ofcrosslinking.

In any of the degradation processes disclosed herein, less than 50% ofthe molecules of the first polymer composition may be branched moleculesprior to contact with the free radical initiator. Conversely, in any ofthe processes, more than 50% of the molecules of the second polymercomposition may be branched molecules.

In one specific embodiment, a process disclosed herein includes adding acrystalline polymer to either the first or second polymer composition.In a specific embodiment, any of the processes may include either: (a)adding a crystalline polymer to form a blend with the random copolymerof the first polymer composition prior to contacting the first polymercomposition with the free radical initiator; or (b) adding a crystallinepolymer to form a blend with the random copolymer of the second polymercomposition after forming the second polymer composition.

With respect to the processes disclosed herein, the first polymercomposition or the second polymer composition, or both, may additionallyinclude a crystalline polymer blended with the random copolymer, thecrystalline polymer having a melting point greater than about 110° C.More narrowly, the crystalline polymer may have a melting point greaterthan about 115° C. Even more specifically, the crystalline polymer mayhave a melting point greater than about 130° C.

In a specific embodiment of the process, the first polymer compositionor the second polymer composition, or both, may additionally include acrystalline polymer blended with the random copolymer, wherein thecrystalline polymer comprises polypropylene or a copolymer comprisingpropylene units and at least one comonomer selected from the groupconsisting of ethylene or C4-C20 alpha-olefins, preferably the groupconsisting of ethylene or C4-C8 alpha-olefins, the copolymer having acomonomer content of less than about 14 mole %.

For example, the comonomer content may be up to about 11 mole % and morepreferably from about 7 mole % to about 11 mole %. The comonomer contentmay be less than about 3 mole %. In a specific embodiment, the propylenecontent of the random copolymer may be about 63 mole % or greater andabout 93 mole % or less. Within that range, for example, the propylenecontent of the random copolymer may be about 60 mole % or greater. Morenarrowly, within that range, the propylene content of the randomcopolymer may be about 73 mole % or greater. Also within theabove-mentioned range, the propylene content of the random copolymer maybe about 89 mole % or less. More narrowly, the propylene content of therandom copolymer may be about 86 mole % or less. More narrowly still,the propylene content of the random copolymer may be about 83 mole % orless

In any of the processes disclosed herein, the crystalline polymer mayinclude isotactic polypropylene. The isotactic polypropylene may, forexample, have a melting point greater than 110° C. More narrowly,isotactic polypropylene may have a melting point greater than 115° C.More narrowly still, the isotactic polypropylene having a melting pointgreater than 130° C.

Preferably, in any of the degradation processes disclosed herein, thefirst polymer composition is fully melted in the presence of the freeradical initiator. When a free radical initiator is used, an effectiveamount of free radical initiator should be contacted with the firstpolymer composition. Preferably, the free radical initiator is presentin an amount sufficient to increase the MFR of the first polymercomposition. More preferably, the free radical initiator is present inan amount sufficient to increase the MFR of the first polymercomposition by at least 100% to form the second polymer composition.

In certain specific embodiments of the degradation process, the firstpolymer composition has an MFR of less than 50 dg/min. at 230° C. Inother specific embodiments, the first polymer composition has an MFR ofless than 40 dg/min. at 230° C. In yet other specific embodiments, thefirst polymer composition has an MFR of less than 30 dg/min. at 230° C.In certain other embodiments of the degradation process, the firstpolymer composition has an MFR of less than 20 dg/min. at 230° C.

As mentioned above, the second polymer composition preferably has an MFRgreater than 250 dg/min. at 230° C. As reflected in the examples below,however, with the present invention, the MFR can be higher than 250dg/min. at 230° C., and for certain specific embodiments, the MFR may begreater than 350 dg/min. at 230° C. For example, the second polymercomposition may have an MFR greater than 500 dg/min. at 230° C. Forcertain processes, the second polymer composition may have an MFRgreater than 600 dg/min. at 230° C. For yet others, the second polymercomposition has an MFR greater than 750 dg/min. at 230° C. In somecircumstances, it is desirable for the second polymer composition tohave an MFR greater than 1,000 dg/min. at 230° C.

Preferably, the crystallinity of the random copolymer is at least about10%. In a specific embodiment, the crystallinity of the random copolymeris preferably no greater than about 40%. In a another specificembodiment, the crystallinity of the random copolymer is no greater thanabout 45%. In yet another specific embodiment, the crystallinity of therandom copolymer is no greater than about 50%.

Certain terms and properties used in characterizing aspects of the highMFR composition will now be defined, as used in this patent and forpurposes of interpreting the scope of the claims.

Semicrystalline Random Copolymer

In certain specific embodiments, the adhesive composition includes a“semicrystalline random copolymer.” The term “random copolymer” as usedherein is defined as a copolymer in which the distribution of themonomer residues is consistent with the random statisticalpolymerization of the monomers, and includes copolymers made frommonomers in a single reactor, but does not include copolymers made frommonomers in series reactors, which are defined herein to be “blockcopolymers.” The random copolymer discussed herein is preferably“semicrystalline,” meaning that in general it has a relatively lowcrystallinity, as will be discussed more specifically below. Thissemicrystalline random copolymer can include, for example, 70-88 mole %propylene units and alpha olefin units having 2 carbon atoms (ethyleneunits) or from 4 to 20 carbon atoms, preferably from 4 to 8 carbonatoms, e.g., butene units or octene units. In a specific embodiment, asemicrystalline random copolymer useful herein is a polypropylenepolymer, specifically a propylene-ethylene copolymer, in which asubstantial number of the copolymer units are propylene units, e.g.,greater than 70 mole %, including such copolymers having 85-90 mole %propylene, or copolymers having 70-88 mole % propylene. Thatsemicrystalline random copolymer is thus distinguishable from copolymersmade of propylene and ethylene units that have fewer than 70 mole %propylene units, including conventional polyethylene polymers havingsome amount of propylene. It has been discovered that superior adhesiveproperties can be obtained using one or more of the semicrystallinerandom copolymers described herein.

The random copolymers may be substantially amorphous, but should becrystallizable and should have a crystallinity of at least about 2% andno greater than about 65%. The crystallinity of the random copolymershould be derived from stereoregular polypropylene sequences. The randomcopolymer may be crystallizable, meaning that they may be amorphous inan undeformed state, but upon stretching or annealing, crystallizationmay occur. In any event, the melting point of the random copolymershould be from about 25 NC to about 105 NC, and preferably less than 100NC. Further, the heat of fusion of the random copolymer should be lessthan 75 J/g as determined by DSC. A variety of comonomers may be used informing the random copolymers described herein. Suitable comonomersinclude ethylene and alpha-olefins, such as C₄-C₂₀ alpha-olefins andpreferably C₄-C₈ alpha-olefins. The alpha-olefin comonomer can be linearor branched, and two or more comonomers can be used, if desired.Examples of suitable comonomers include ethylene, linear C₄-C₈alpha-olefins, and alpha-olefins having one or more C₁-C₃ alkylbranches. Specific examples include ethylene; 3-methyl-1-butene;3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl,ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl orpropyl substituents; 1-heptene with one or more methyl, ethyl or propylsubstituents; 1-octene with one or more methyl, ethyl or propylsubstituents; 1-nonene with one or more methyl, ethyl or propylsubstituents; ethyl, methyl or dimethyl-substituted 1-decene, or1-dodecene. Preferred comonomers include ethylene, 1-butene, 1-pentene,3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,3,3-dimethyl-1-butene, 1-heptene, 1-hexene with a methyl substituent onany of C₃-C₅, 1-pentene with two methyl substituents in anystoichiometrically acceptable combination on C₃ or C₄,3-ethyl-1-pentene, 1-octene, 1-pentene with a methyl substituent on anyof C₃ or C₄, 1-hexene with two methyl substituents in anystoichiometrically acceptable combination on C₃-C₅, 1-pentene with threemethyl substituents in any stoichiometrically acceptable combination onC₃ or C₄, 1-hexene with an ethyl substituent on C₃ or C₄, 1-pentene withan ethyl substituent on C₃ and a methyl substituent in astoichiometrically acceptable position on C₃ or C₄, 1-decene, 1-nonene,1-nonene with a methyl substituent on any of C₃-C₉, 1-octene with twomethyl substituents in any stoichiometrically acceptable combination onC₃-C₇, 1-heptene with three methyl substituents in anystoichiometrically acceptable combination on C₃-C₆, 1-octene with anethyl substituent on any of C₃-C₇, 1-hexene with two ethyl substituentsin any stoichiometrically acceptable combination on C₃ or C₄, and1-dodecene. It should be appreciated that the list of comonomers aboveis merely exemplary, and is not intended to be limiting. A particularlypreferred comonomer is ethylene.

Crystallinity

Another property that can be used to characterize the semicrystallinerandom copolymer is its crystallinity, which as discussed above isrelatively low. As discussed below, the semicrystalline random copolymerused in specific embodiments of this invention preferably has acrystallinity of from 2% to 65% of the crystallinity of isotacticpolypropylene. Without being bound by theory, it is contemplated thatthe relatively low crystallinity of the random copolymer provides Theterm “crystalline” as used herein broadly characterizes those polymersthat possess a high degree of both inter and intra molecular order, andwhich preferably melt higher than 110° C., more preferably higher than115° C., and most preferably above 130° C. A polymer possessing a highinter and intra molecular order is said to have a “high” level ofcrystallinity, while a polymer possessing a low inter and intramolecular order is said to have a “low” level of crystallinity.Crystallinity of a polymer can be expressed quantitatively, e.g., interms of percent crystallinity, usually with respect to some referenceor benchmark crystallinity. As used herein, crystallinity is measuredwith respect to isotactic polypropylene homopolymer. Preferably, heat offusion is used to determine crystallinity. Thus, for example, assumingthe heat of fusion for a highly crystalline polypropylene homopolymer is190 J/g, a semicrystalline random copolymer having a heat of fusion of95 J/g will have a crystallinity of 50%. The term “crystallizable” asused herein refers to those polymers or sequences that are mainlyamorphous in the undeformed state, but upon stretching or annealing,become crystalline. Thus, in certain specific embodiments, thesemicrystalline random copolymer can be crystallizable.

Polypropylene

The crystalline polymer is preferably a polypropylene polymer, wherein“polypropylene” is defined according to its conventional meaning. Thepolypropylene disclosed herein may be a homopolymer, in which thepolymer is made up entirely of propylene sequences (also referred tointerchangeably as “segments” or “units”). A propylene may also be acopolymer. For example, a polypropylene copolymer may be prepared bypolymerizing propylene with a C₂ or C₄-C₂₀ alpha olefin, preferably byreacting propylene and ethylene in the presence of a chiral metallocenecatalyst with an activator and optional scavenger. The comonomer usedwith propylene may be linear or branched. Preferred linear alpha-olefinsinclude ethylene or C₄ to C₂₀ alpha olefins and preferably C₄ to C₈alpha olefins, more preferably ethylene, 1-butene, 1-hexene, and1-octene. Preferred branched alpha-olefins include 4-methyl-1-pentene,3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene.

Preferred polypropylene copolymers have an average propylene content ona molar basis of from about 70 mole % to about 98 mole %, morepreferably from about 85 mole % to about 97 mole %, most preferably fromabout 90 mole % to about 96 mole %. The balance of the copolymer is oneor more alpha-olefins as specified above and optionally minor amounts ofone or more diene monomers.

Preferably, the polypropylene copolymer comprises ethylene as thecomonomer in the range of from about 2 to 30 mole %, more preferablyfrom about 3 to about 15 mole % ethylene, and most preferably from about4 to 10 mole % ethylene.

The use of a chiral metallocene catalyst ensures that the methyl groupof the propylene residues have predominantly the same tacticity. Bothsyndiotactic and isotactic configuration of the propylene are possiblethough the isotactic polymers are preferred. The tacticity of thepropylene residues leads to crystallinity in the polymers. For thepolymers of the present invention the low levels of crystallinity in thepolypropylene copolymer are derived from isotactic polypropyleneobtained by incorporating alpha-olefin comonomers as described above.The semi-crystalline polypropylene copolymer preferably has a heat offusion from about 30 J/g to about 80 J/g, more preferably from about 40J/g to about 70 J/g, and most preferably from about 50 J/g to about 65J/g. The crystallinity of the polypropylene copolymer arisespredominantly from crystallizable stereoregular propylene sequences. Thecrystallinity of the polypropylene copolymer can also be expressed interms of percentage of crystallinity. For example, to the extent thethermal energy for the highest order of polypropylene is 190 J/g, 100%crystallinity would be equal to 190 J/g. Accordingly, the aforementionedheat of fusion values would provide a polypropylene crystallinity offrom about 10% to about 45%, more preferably from about 20% to about40%, and most preferably from about 25% to about 35%.

The polypropylene copolymer preferably has a single broad meltingtransition. Typically a sample of the polypropylene copolymer will showsecondary melting peaks adjacent to the principal peak, these areconsidered together as a single melting point. The highest of thesepeaks is considered the melting point. The polypropylene copolymerpreferably has a melting point of from about 25° C. to about 120° C.,preferably in the range of from about 30° C. to about 110° C., morepreferably in the range of from about 65° C. to about 100° C.

The weight average molecular weight of the polypropylene copolymer canbe between 5,000 to 200,000 Daltons, preferably 50,000 to 150,000, witha MWD (M_(w)/M_(n)) between 1.5 to 40.0, more preferably between about1.8 to 5 and most preferably between 1.8 to 3.

The length and distribution of stereoregular propylene sequences inpreferred polypropylene copolymers is consistent with substantiallyrandom statistical copolymerization. It is well known that sequencelength and distribution are related to the copolymerization reactivityratios. By substantially random, we mean copolymer for which the productof the reactivity ratios is generally 2 or less. In stereoblockstructures, the average length of polypropylene sequences is greaterthan that of substantially random copolymers with a similar composition.Prior art polymers with stereoblock structure have a distribution ofpolypropylene sequences consistent with these blocky structures ratherthan a random substantially statistical distribution. To produce acrystallizable copolymer with the required randomness and narrowcomposition distribution, it is desirable to use (1) a single sitedcatalyst and (2) a well-mixed, continuous flow stirred tankpolymerization reactor which allows only a single polymerizationenvironment for substantially all of the polymer chains of preferredpolypropylene copolymers.

Preferred polypropylene copolymers of this embodiment are prepared bypolymerizing propylene and at least one C₂ or C₄-C₂₀ alpha olefin in thepresence of a chiral metallocene catalyst with an activator and optionalscavenger. Preferred chiral metallocenes are those known to favorincorporation of propylene for the production of predominantly isotacticpolypropylene pentads and statistically random incorporation of theα-olefin comonomer(s). The term “metallocene” and “metallocene catalystprecursor” are terms known in the art to mean compounds possessing aGroup IV, V, or VI transition metal M, with a cyclopentadienyl (Cp)ligand or ligands which may be may be substituted, at least onenon-cyclopentadienyl-derived ligand X, and zero or oneheteroatom-containing ligand Y, the ligands being coordinated to M andcorresponding in number to the valence thereof. The metallocene catalystprecursors generally require activation with a suitable co-catalyst(referred to as activator) in order to yield an active metallocenecatalyst which refers generally to an organometallic complex with avacant coordination site that can coordinate, insert, and polymerizeolefins.

Preferable metallocenes are cyclopentadienyl (Cp) complexes which havetwo Cp ring systems for ligands. The Cp ligands preferably form a bentsandwich complex wh the metal and are preferably locked into a rigidconfiguration through a bridging group. These cyclopentadienyl complexeshave the general formula:

(Cp¹R¹ _(m))R³ _(n)(Cp²R² _(p))MX_(q)

Wherein Cp¹ of ligand (Cp¹R¹ _(m)) and Cp² of ligand (Cp²R² _(p)) arepreferably the same, R¹ and R² each is, independently, a halogen or ahydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid orhalocarbyl-substituted organometalloid group containing up to 20 carbonatoms, m is preferably 1 to 5, p is preferably 1 to 5, and preferablytwo R¹ and/or R² substituents on adjacent carbon atoms of thecyclopentadienyl ring associated there which can be joined together toform a ring containing from 4 to 20 carbon atoms, R³ is a bridginggroup, n is the number of atoms in the direct chain between the twoligands and is preferably 1 to 8, most preferably 1 to 3, M is atransition metal having a valence of from 3 to 6, preferably from group4, 5, or 6 of the periodic table of the elements and is preferably inits highest oxidation state, each X is a non-cyclopentadienyl ligand andis, independently, a hydrocarbyl, oxyhydrocarbyl, halocarbyl,hydrocarbyl-substituted organometalloid, oxyhydrocarbyl-substitutedorganometalloid or halocarbyl-substituted organometalloid groupcontaining up to 20 carbon atoms, q is equal to the valence of M minus2.

Numerous examples of the biscyclopentadienyl metallocenes describedabove for the invention are disclosed in U.S. Pat. Nos. 5,324,800;5,198,401; 5,278,119; 5,387,568; 5,120,867; 5,017,714; 4,871,705;4,542,199; 4,752,597; 5,132,262; 5,391,629; 5,243,001; 5,278,264;5,296,434; and 5,304,614, all of which are incorporated by reference forpurposes of U.S. patent practice.

Illustrative, but not limiting examples of preferred biscyclopentadienylmetallocenes of the type described in group 1 above for the inventionare the racemic isomers of:

μ-(CH₃)₂Si(indenyl)₂M(Cl)₂ μ-(CH₃)₂Si(indenyl)₂M(CH₃)₂μ-(CH₃)₂Si(tetrahydroindenyl)₂M(Cl)₂μ-(CH₃)₂Si(tetrahydroindenyl)₂M(CH₃)₂ μ-(CH₃)₂Si(indenyl)₂M(CH₂CH₃)₂μ-(C₆H₅)₂C(indenyl)₂M(CH₃)₂;

Wherein M is chosen from a group consisting of Zr, Hf, or Ti.

In another embodiment, the polymer component can be a blend of discretepolymers. Such blends can be of two or more polypropylene copolymers(e.g., as described above), where each of the components of the polymerblend would individually qualify as a polymer component.

It is understood in the context of the present invention that, in one ormore embodiments, more than one polymer component may be used in asingle blend. Each of the polymer components is described above and thenumber of polymer components in this embodiment is less than three andmore preferably, two.

Adhesive Compositions

Preferably, the compositions of this invention are adhesivecompositions. Preferably, the adhesive composition includes one or moreadditives, such as tackifiers, plasticizers (extender oils), waxes,colorants, antioxidants, fillers and others conventionally used inadhesive blends, which are discussed above. More preferably, theadhesive composition comprises from 0 to about 80 weight percent of atleast one tackifier; from 0 to about 60 weight percent of at least oneplasticizer; and from 0 to about 50 weight percent of at least one wax;from 0 to about 5 weight percent of an anti-oxidant, wherein the sum ofthe components (b), (c), and (d) comprises from about 5 to about 95weight percent of said adhesive composition.

Suitable plasticizers or extender oils include aromatic, naphthenic,paraffinic, or hydrogenated (white) oils and mixtures thereof. One ofthe particular advantages of the invention is that none or only minoramounts of extender oils may be required to achieve good flow andcoating characteristics because of the inherently low melt viscosityproperties of the adhesive of the invention. Reduction in the level ofextender oil required to process the composition tends to result inimproved cohesiveness of the adhesive and reduces bleed out of theextender. Where used, the extender oil is added at a level from about0.5 to about 25 parts by weight per hundred parts by weight of the SCP,more preferably from about 5 to 15 parts by weight.

As indicated above, the components forming the adhesive formulations ofthe invention have properties such that adhesives having a very low meltviscosity are provided, thereby facilitating flow of the adhesivethrough the coating apparatus, e.g., coating die, without resorting tothe inclusion of solvents or excess extender oil into the composition.Melt viscosities of less than 10,000 centipoise measured at 180° C. perASTM D 3236 can be readily achieved for the adhesive blend. The morepreferred melt viscosity at 180° C. is less than 2,000 cps and the mostpreferred melt viscosity at 180° C. is approximately 1500 cps.

Typical industrial applications include packaging, particularly for lowtemperature use such as for dairy products or for freezer packaging offood products, and in sanitary disposable consumer articles, forexample, diapers, feminine care pads, napkins, etc. However, even moretraditional end use applications such as book-binding, wood working andlabeling will also benefit from both the low temperature flexibility,heat resistance and the efficiency of end use in automated means ofapplying the invention compositions to the various art-recognizedsubstrates or adherends. In a preferred embodiment, the adhesivecompositions of the present invention are hot melt adhesives. In anotherembodiment, other polyolefins, preferably isotactic polypropylenes, suchas Achieve™ 3866G, commercially available from ExxonMobil Chemical Co.,Baytown, Tex., can be used as blend components in the adhesivecomposition of the present invention.

The hot melt adhesive compositions may be applied to the desiredsubstrate or adhered in any manner known in the art, particularly thosemethods used traditionally for packaging. Typically a coating head ornozzle, with associated equipment, for example those manufactured byNordson Corporation, Duluth, Ga., are used. The compositions can beapplied as fine lines, dots or spray coatings, in addition to othertraditional forms as desired.

Degradation

The term “degradation” as used herein refers to the process by which themelt flow rate of a material is increased, reflecting a lowering ofmolecular weight. Another term that is deemed to mean the same thing as“degraded” herein is “modified.” Preferably, a free radical initiator isused to cause the increase in MFR. A polymer is modified or degraded inaccordance with this invention when the polymer, or a blend of polymers,is treated with a free radical initiator, e.g., peroxide, preferablywhile the polymer is in a melted state, more preferably in a fullymelted state. Preferably, the degradation of this invention involvescontrolled chain scission. For example, when a free radical initiator isused, free radicals of the polymers being treated are produced bythermal scission of the peroxide. Other sources of free radicals such asdiazo compounds may also be utilized. In any case, it is contemplatedthat the free radicals produced from the initiator (e.g., peroxide)abstract the tertiary hydrogen on the propylene residue of the randomcopolymers. The resulting free radical disproportionates to two lowermolecular weight chains, one with an olefin near the terminus and theother a saturated polymer. This process can continue with the generationof successively lower molecular weight polymers. Since the site of theattack and scission of the chains is random, the distribution of themolecular weight of the resulting degraded polymer approaches the mostprobable (PDI=2) irrespective of the PDI of the initial polymer, where“PDI” refers to Polydispersity Index, defined as Mw/Mn, where Mw and Mnare measured by GPC. Thus, under the appropriate conditions, chainscission is initiated to cause degradation of the polymer or polymerblend.

Another process that may occur during degradation, and that competeswith chain scission, is crosslinking. In a crosslinking reaction, thefree radicals combine to form branched macromolecules of highermolecular weight. Eventually, this synthesis reaction may lead tovulcanization of the polymer. In copolymers of ethylene and propylene,this balance of crosslinking and degradation is mainly dependent on thecomposition of the copolymer. Since the degradation reaction is uniquelyassociated with the propylene residues, lower amounts of propylene inthe copolymer tend to favor crosslinking over degradation. However, itshould be recognized that the scission and crosslinking reactions arenot mutually exclusionary. That is, even during degradation, some amountof branching may occur. However, because the branching and scissionreactions are random, these complementary processes should not lead toan increase in PDI. However, a polymeric material degraded as discussedherein preferably has a majority of branched molecules. The amount ofbranching depends on a number of variables, primarily the reactionconditions, the composition of the polymers and the extent ofdegradation. Random copolymers having a higher ethylene content shouldgenerate a higher level of branching than those with a lower ethylenecontent. When the increase in MFR is small (factor of 2 or 3), then theextent of branching in the resulting polymer should be minor. However,when the extent of degradation of the polymer is relatively large (e.g.,ratio of final to starting MFR is 20 or greater), then the amount ofbranching in the low molecular weight materials should be considerable.Thus, in certain embodiments of this invention, the rate or extent ofdegradation is to substantially proportional to the relative amounts ofpropylene and ethylene sites. For example, if too many ethylene sitesare present, the use of the peroxide or other free radical initiator mayresult in crosslinking rather than chain scission, and the materialbeing treated will not degrade to a higher MFR. Thus, an importantaspect of certain specific embodiments of this invention relates to therelative amounts of the polymers used in the blend. It is recognized bythe inventors that the random copolymer and a polypropylene degradeindependently. It is contemplated that the polypropylene degrades fasterthan the random copolymer under similar conditions. Thus, a blend ofrandom copolymer and polypropylene with change in PDI during thedegradation procedure with the polypropylene degrading to a lowermolecular weight sooner than the random copolymer.

Techniques for determining the molecular weight (Mn and Mw) andmolecular weight distribution (MWD) are found in U.S. Pat. No. 4,540,753(Cozewith, Ju and Verstrate) (which is incorporated by reference hereinfor purposes of U.S. practices) and references cited therein and inMacromolecules, 1988, volume 21, p 3360 (Verstrate et al) (which isherein incorporated by reference for purposes of U.S. practice) andreferences cited therein. Unless specifically identified, any one ofthose techniques may be used.

MFR (Melt Flow Rate) of the grafted and ungrafted material was measuredaccording to ASTM D1238 at 230° C.

Mooney viscosity of the grafted and ungrafted material was measuredaccording to ASTM D1646, [ML(1+4), 125° C.].

EXAMPLES

The following examples are presented to illustrate aspects and featuresof specific embodiments of the invention. All parts, proportions andpercentages are by weight unless otherwise indicated. Although theexamples may be directed to certain embodiments of the presentinvention, they are not to be viewed as limiting the invention in anyspecific respect.

Example 1 Catalyst Activation

In this example, Catalyst A, μ-Me₂Si(Indenyl)₂HfMe₂ (70.8 mg, 0.1430mmole) (Cat. A) was preactivated withdimethylanilinium-tetrakis(pentafluorophenyl)borate [DMAH⁺ B(pfp)4⁻](110.1 mg, 0.137 mmole) in toluene (900 mL) under an inert atmosphere.This mixture was allowed to activate until the evolution of methanestopped (5-10 min.) and then sealed for transfer to the delivery vessel.The catalyst solution was pumped to the reactor from the vessel at acontrolled rate using a calibrated HPLC pump.

Copolymer Synthesis

A mixture of hexanes (5.4 L/h) was pumped into a 1 liter, liquid filled,stirred tank reactor while the temperature was equilibrated at 50° C.using a steam/water mixture flowing through the reactor jacket. Thepreactivated Cat A in toluene (0.078 L/h, 0.0119 mmole/h) and ascavenger solution of triisobutylaluminum in hexane (0.060 L/h, 0.1955mmole/h) were then pumped to the reactor for 20 min before monomers wereintroduced. Propylene (0.7778 L/h, 10 mole/h) was pumped to the reactoras a liquid. Ethylene was delivered as a gas solubilized in the chilledsolvent in a controlled fashion through a mass flow meter/controller(19.8 g/h, 0.7071 mole/h). Continuous flow was established at a constanttemperature and stirring. Onset of polymerization activity wasdetermined by an observation of a viscous product. Once activity wasestablished, one hour was provided to establish equilibrium. Theresulting mixture, containing mostly solvent, polymer (6.19 wt %), andunreacted monomers was collected (1.0 h) in a can containing somealcohol to end the polymerization activity. A stabilizer was added tothe polymer solution and mixed. The solvent was evaporated on a steambath and the product dried under vacuum at 90° C. for 16 h. Theresulting solid (220 g) showed 17.1 mol % ethylene by FourierTransformation Infrared analysis (FTIR) (within the parameters set byASTM D-3900), 1.5 Mooney Viscosity, 124,400 Daltons weight averagemolecular weight (Gel Permeation Chromatography (GPC) with Low AngleLaser Light Scattering Detector, hereafter referred to as LALLS) andmolecular weight distribution (MWD) 1.79. The polymer solid is hereindesignated as Sample No. 1.

Example 2

In this example, Catalyst A was preactivated and used as described aboveto make a similar propylene based copolymer (Sample No. 2) with aslightly different composition. Reaction conditions were identical toabove with the following modifications: ethylene was delivered as a gassolubilized in the chilled solvent in a controlled fashion through amass flow meter/controller (12 g/h, 0.4286 mole/h). The resultingpolymer solution was collected for 4 hours. After workup the resultingsolid (720 g) showed a melting endotherm by DSC of 87.7° C., a glasstransition (Tg) of −19.3° C., and a heat of fusion of 56.6 J/g. FTIRshowed 12.0 mol % ethylene and the Mooney viscosity was 2.9. The weightaverage molecular weight (GPC with LALLS Detector) was 183,200 Daltonsand the MWD was 1.77. The polymer was characterized to give Mooneyviscosity (by Mooney Viscometer, ASTM D1648), ethylene content (by FTIR,ASTM D3900 or, for ethylene contents below 50 mol %, a modified D3900),ENB content (by FTIR, ASTM D6047), melt temperature and/or glasstransition temperature (by DSC, described herein), and molecular weight(by GPC, described herein).

Example 3

In this example, Catalyst A (21 mg, 0.042 mmol) was prepared in the samegeneral manner as Example 1. It was preactivated withdimethylanilinium-tetrakis(pentafluorophenyl)borate [DMAH⁺ B(pfp₄)] (30mg, 0.037 mmol) in toluene (75 mL) under an inert atmosphere. Themixture was allowed to equilibrate until complete solution was achieved(approximately 20 minutes). To the solvent-filled reactor, catalystsolution was pumped for approximately 5 minutes (34.8 mL/hr, 0.0197mmol/hr) before a feed solution, composed of hexanes (11,250 mL),propylene (3,750 mL, 45.8 moles), triisobutylaluminum (25 wt. % inheptane, 4.64 mL) and ethylene (20 psig over 100 psig nitrogen), waspumped at a rate of approximately 100 mL/min. After equilibration at 75°C. for 30 minutes, the effluent from the reactor was collected for 72minutes in three aliquots. Devolatization of the obtained mixtureyielded a total of 636.4 g of solid product. (Sample No. 3) The productshowed 8.2 mol % ethylene by FT-IR, melt viscosity of 152,900 cps at190° C. (average of three aliquots), 98,100 Daltons weight averagemolecular weight and MWD of 1.68.

Example 4

In this example, dimethylsilandiylbis(2-methyle-4-phenyl-1-indenyl)zirconium dimethyl (150 mg, 0.255 mmol) was activated in the mannerdescribed above in Example 1 withdimethylanilinium-tetrakis(pentafluorophenyl)borate [DIMAH⁺ B(pfp₄)](210 mg, 0.262 mmol) in toluene (900 mL) under an inert atmosphere. Themixture was allowed to equilibrate with stirring until complete solutionwas achieved (approximately 20 minutes). Hexanes were pumped (6.0 L/hr)into the 0.5 liter, liquid-filled, stirred tank reactor while thetemperature was equilibrated to 80° C. using steam/water flowing throughthe reactor jacket. The pre-activated catalyst solution (9.0 mL/hr,0.0255 mmol/hr) and scavenger (51.6 mL/hr, 0.128 mmol/hr) were pumpedinto the reactor for approximately 20 minutes before introduction of themonomers. Propylene (774 g/hr, 18.4 mol/hr) and 1-hexene (114 g/hr,0.738 mol/hr) were introduced to the reactor as a chilled solution inthe hexanes solvent stream. Commencement of polymerization activity wasevidenced by a drop in the temperature of the water entering the reactorjacket. Continuous flow was established at a constant temperature withstirring. After the onset of polymerization, a minimum of 30 minutes wasallotted for the establishment of steady state conditions. The effluent,consisting of solvent, unreacted monomers, and polymer, was collectedfor 60 minutes. Devolatilization of the obtained mixture yielded a totalof 742.0 g of solid product. The product showed a melt viscosity of21,550 cps @ 190° C. (Sample L).

Adhesive Testing

A number of hot melt adhesive compositions were prepared by blending thepolymer, tackifier, antioxidant, and other ingredients such asplasticizer oil, wax, liquid resin tackifiers, etc. under low or highshear mixing at elevated temperatures to form a fluid melt. Mixingtemperatures varied from about 130° C. to about 200° C., preferably fromabout 150° C. to about 180° C. In evaluating the performancecharacteristics of the adhesive compositions shown in Tables 3 through6, test procedures “a” through “e” were employed:

-   -   a.) Adhesive Melt Viscosity (ASTM D-3236)—Melt viscosity        profiles were measured at temperatures between 130° C. and        180° C. using a Brookfield Thermosel viscometer.    -   b.) Peel Strength (modified ASTM D1876)—Substrates (1×3 inches))        were heat sealed with adhesive film (5 mils in thickness) at        135° C. for 1 to 2 sec. and 40 psi. pressure. Bond specimens        were peeled back in a tensile tester at a constant crosshead        speed of 12 in/min. The average force required to peel the bond        (5 specimen) apart was recorded.    -   c.) Shear Adhesion Fail Temperature (SAFT) (modified D4498)        measures the ability of a bond to withstand an elevated        temperature rising at 10° F./15 min., under a constant force        that pulls the bond in the shear mode. Bonds 1 inch by 1 inch        (Kraft paper) were formed of adhesive by heat sealing as in        procedure “a.)” for 1.5 sec. The test specimens were suspended        vertically in an oven at 32° C. with a 500 gram load attached to        the bottom. The temperature at which the weight fell was        recorded. Adhesives possessing high failure temperature are        essential for the assembly of disposable articles or packaging        goods that are often subjected to very high temperatures during        storage and shipping.    -   d.) Tensile Strength and Elongation (ASTM D412 and ASTM D638)-75        mil pads were made and measured according to the ASTM procedures        D412 and D638.    -   e.) ASTM E1356-95 was use for measuring the glass transition        temperature of polymers (elastomers or plastics).

Hot Melt Adhesive Performance

A number of propylene-based copolymers (see Tables 3 and 4 for physicalcharacteristics) were compounded with tackifiers, oil or wax and atleast one stabilizer to form hot melt adhesive blends (see Tables 5 and8). The properties of these blends were tested against typical blendscontaining EVA, SIS, SBS, LDPE (see Tables 5, 6, 7 and 8). Data inTables 7 and 8 illustrate the effect of a low molecular weight isotacticpolypropylene to induce crystallization. The data in Table 9 illustratethe performance of adhesive blends containing C₃/C₆ copolymers.

The semi-crystalline polymer (SCP) C₃/C₂ based hot melt adhesive (HMA)blends of the present invention exhibited several advantages overtypical styrenic block copolymer disposable adhesive systems (see Table5 and 8). The melt viscosities were indicative of the molecular weightof the copolymer. For example, the SCP based HMA blends having relativemelt viscosities (i.e. Formulation 8 vs. SBS and SIS) had higher peelstrengths in addition to higher tensile (cohesive) strength, and heatresistance (Shear Adhesion Failure Temperature (SAFT)), whilemaintaining comparable elongation. In the same fashion, C₃/C₆ copolymersalso compared favorably to SBS- and SIS-based formulations (i.e. Table9, formulation 28 vs. SBS and SIS in Table 3).

Both C₃/C₂ and the C₃/C₆ SCP based HMA blends demonstrated superior heatresistance (SAFT) and higher tensile strength versus metallocenecatalyzed EXACT plastomers (see Tables 6 and 9). The C₃/C₂ and C₃/C₆ SCPbased HMA blend systems also had superior peel strength, tensilestrength, and elongation versus amorphous propylene-butene polymers suchas REXTAC™ 2715 (see Tables 6 and 9).

Both tensile strength and SAFT were improved when small amounts ofisotactic polypropylene (iPP) were added to the SCP based HMA blends(Tables 7, 8 and 9). The C₃/C₂ SCP based HMA blend systems also showedimproved flexibility (elongation) and bond strength versus EVA basedpackaging formulations (see Table 8). Deficient elongation of C₃/C₆ SCPbased blends was likely due to low SCP molecular weights (low meltviscosities, formulations 31 and 32, Table 9). Nonetheless, theseformulations showed superior tensile strengths. One skilled in the artmay blend the preferred additives stated in the present disclosure withformulations 21 and 22 to achieve comparable viscosity levels withformulations 23 and 24 and still expect to maintain superior tensilestrength, peel strength, and elongation due to the presence of thedisclosed isotactic polypropylene and SCP in the hot melt adhesive.

Hot melt adhesive blends may also be obtained with little modification.Formulation 30, comprised mainly of C₃/C₆ SCP, demonstrates superiortensile strength, elongation and heat resistance. One skilled in the artmay blend the preferred additives stated in the present disclosure withformulation 30 to achieve improved adhesion while maintaining acceptablemelt viscosity, tensile strength, and elongation.

TABLE 1 Reactor Conditions Cement Poly C₂ C₃ Cat A C₃ Catalyst Scav/CatConc Rate Temp Feed Feed Feed Conversion Efficiency Ratio Sample # (%)(g/h) (° C.) (g/h) (g/h) (g/h) (%) (g/g) (mol/mol) A 6.19 230.5 51 20420 0.0059 48.2 39115 16.4 B 6.52 246.4 51 12 420 0.0059 53.8 41822 16.4C — 525.0 75 99 816 0.0097 60.0 54124 93.6 D — 490.2 80 99 816 0.014660.1 33575 62.4 E — 444.0 90 74 816 0.0203 51.4 21872 44.9 F — 435.0 8099 816 0.0077 50.4 56494 117.6 G — 489.0 80 74 816 0.0097 57.3 5041293.6 H — 458.4 85 124 816 0.0146 53.1 31397 62.4 I — 546.6 80 74 8160.0175 64.6 31234 52.1 J — 586.2 85 124 816 0.0214 68.7 27393 42.6 K —607.2 85 148 816 0.0233 69.6 26060 39.1 Cement Conc.: % of polymerdissolved in solution Scav/Cat Ratio = scavenger/catalyst ratio

TABLE 2 Reactor Conditions for Propylene-Hexene Copolymers C₃ C₆ CatCatalyst Scav/Cat Poly Rate Temp Feed Feed Feed Efficiency Ratio Sample# (g/h) (° C.) (g/h) (g/h) (g/h) (g/g) (mol/mol) L 742.2 80 774 1140.0150 49,490 4.99 M 736.2 83 774 114 0.0150 49150 4.99 N 741.6 76 774 93 0.0150 49,490 4.99 O 670.2 79 774 138 0.0150 44,728 4.99 P 775.0**90 720  165** 0.0164**  48,534** 4.84 *Blend of four aliquots(21517-024-004, -005, -006, and -008). **Average values.

TABLE 3 SCP based HMA blend Physical Properties Mol ΔH (J/g) GPC Sam- %Tm, (Heat of MI Mn Mw ple # C₂ ° C. fusion) (dg/min) (×10³⁾ (×10³) Mw/MnA 17.13 — — (1.5)* 69.4 124.4** 1.79 B 12.0 88 56.6 (2.9)* — 183.2**1.77 C 8.16 82 52.9 54 58.6 98.1 1.68 D — 82 43.3 328 40.1 66.9 1.81 E5.26 100 62.4 507 31.6 58.4 1.85 F 8.53 80 53.1 68 57.6 95.2 1.65 G 5.91102 54.2 81 53.7 93.2 1.74 H 5.35 88 60.1 197 42.6 72.1 1.69 I 5.90 10975.6 209 43.1 76.4 1.77 J 6.83 93 59.0 368 36.8 63.8 1.73 K 10.4 79 48.3289 35.6 64.0 1.80 All the spectra were obtained at a temperature rateof 10 deg/min as described in the present application *Mooney viscosityat 125° C. **GPC-LALLS

TABLE 4 C₃/C₆ Physical Properties ΔH (J/g) Melt (Heat of Viscosity, MnMw Mz Sample # Mol % C₆ T_(m), ° C. fusion) cps @ 190° C. (×10³) (×10³)(×10³) L 102 96.1 21,550 M 101 76.1  8,513 N 107 96.6 35,300 O  93 58.566,000 P*   99** 60.8**    2230** *Blend of four aliquots(21517-024-004, -005, -006, and -008). **Average values.

TABLE 5 Evaluation of SCP based HMA blends in a Disposable ProductFormulation FORMULATION # Sample # 1 2 3 4 5 T_(m)/MI Typical SISPerforming 100 wt % — — — — — Adhesives¹ Typical SBS Performing 100 wt %— — — — — Adhesives² A  72/ca 1 30 — — — — B  91/ca 1 — 30 — — — C 81/54 — — 30 — — D  84/328 — — — 30 — E 102/507 — — — — 30 F  87/68 — —— — — G 101/81 — — — — — H  89/197 — — — — — I 105/209 — — — — — J 94/368 — — — — — K  78/237 — — — — — ESCOREZ ™ 5380³ — — 50 50 50 50 50KAYDOL ™ Oil⁴ — — 20 20 20 20 20 IRGANOX ™ 1010⁵ — — 0.25 0.25 0.25 0.250.25 TEMP Viscosity, cps 140° C. 4288 3625 106,750 99,750 13,400 2,5501,858 150° C. 2440 2380 72,300 68,100 9,300 1,805 1,325 160° C. 16101620 52,300 49,400 6,763 1,318 978 170° C. — — 38,100 35,700 5,050 955740 180° C. — — 29,050 27,300 3,830 770 585 Tensile Strength, psi 94 90411 260 232 57 174 Elongation, % 1940 1850 1860 970 1094 211 270Substrate 180° Peel Str, pli Al³ 4.6 5.0 7.7 6.9 4.2 4.7 2.4 PP⁴ 4.3 3.97.6 8.8 6.9 5.4 1.8 PE⁵ 4.7 4.6 7.5 3.9 2.2 5.1 0.4 SAFT to Kraft, ° C.,74 54 73 88 78 65 75 (1″ × 1″, 500 g) FORMULATION # Sample # 6 7 8 9 1011 T_(m)/MI Typical SIS Performing — — — — — — Adhesives¹ Typical SBSPerforming — — — — — — Adhesives² A  72/ca 1 — — — — — — B  91/ca 1 — —— — — — C  81/54 — — — — — — D  84/328 — — — — — — E 102/507 — — — — — —F  87/68 30 — — — — — G 101/81 — 30 — — — — H  89/197 — — 30 — — — I105/209 — — — 30 — — J  94/368 — — — — 30 — K  78/237 — — — — — 30ESCOREZ ™ 5380³ 50 50 50 50 50 50 KAYDOL ™ Oil⁴ 20 20 20 20 20 20IRGANOX ™ 1010⁵ 0.25 0.25 0.25 0.25 0.25 0.25 TEMP Viscosity, cps 140°C. 10,225 11,375 3,830 3,663 2,410 2,885 150° C. 7,125 7,900 2,705 2,5951,698 2,050 160° C. 5,163 5,763 1,975 1,885 1,245 1,493 170° C. 3,8254,275 1,480 1,418 930 1,125 180° C. 2,950 3,250 1,140 1,093 713 870Tensile Strength, psi 201 405 252 212 178 92 Elongation, % 869 1050 928309 360 257 Substrate 180° Peel Str, pli Al³ 6.9 3.6 3.9 2.4 3.7 5.1 PP⁴5.1 10.1 5.8 5.6 5.1 7.4 PE⁵ 5.0 2.8 2.7 1.1 3.2 6.1 SAFT to Kraft, °C., 79 89 78 89 76 57 (1″ × 1″, 500 g) ¹Formulation: 22/58/20 blend ofVECTOR 4215, ESCOREZ 5400, KAYDOL oil ²Formulation: 20/60/20 blend ofVECTOR 4461, ESCOREZ 5600, KAYDOL oil ³Al = aluminum ⁴PP = polypropylene⁵PE = polyethylene

TABLE 6 SCP Polymers vs. Other Polyolefin Polymers in a Hot MeltAdhesive FORMULATION # 12 13 14 7 6 3 15 Sample # EXACT ™ 4023 (125 30 —— — — — — MI/0.882) EXACT ™ 4040 (50 — 30 — — — — — MI/0.885) EXACT ™4038 (125 — — 30 — — — — MI/0.885) REXTAC ™ 2715 — — — — — — 100 SampleG — — — 30 — — — Sample F — — — — 30 — — Sample C — — — — — 30 —ESCOREZ ™ 5400 50 50 50 — — — — ESCOREZ ™ 5380 — — — 50 50 50 — KAYDOL ™OIL 20 20 20 20 20 20 — IRGANOX ™ 1010 — — — — — — — MELT VISCOSITY, cps130° C. 18,025 21,400 10,552 11,375 10,225 13,400 — 140° C. 12,82515,150 7,475 7,900 7,125 9,300 13,625 150° C. 9,325 11,025 5,475 5,7635,163 6,763 4,963 160° C. 6,875 8,275 4,088 — — — 3,650 SAFT, ° C., (1″× 1″, 56.9 58.3 56.9 89 79 78 80 500 g) TENSILE STRENGTH, 81.6 62.3 45.3405 201 232 78 psi ELONGATION, % 1294 1218 342 1050 869 1094 102 PEELSTRENGTH, pli Aluminum 11.7 11.8 8.2 3.6 6.9 4.2 2.2 Polypropylene 16.111.9 5.8 10.1 5.1 6.9 1.1 Polyethylene 12.8 9.8 6.5 2.8 5.0 2.2 4.4EXACT ™ 4040, 4023, 4038, ESCOREZ ™ 5400, and 4038 are trademarks of theExxon Chemical Company. REXTAC ™ 2715 is commercially available fromRexene, having a crystallinity of less than 9 J/g.

TABLE 7 Effect of iPP Nucleating Agent in SCP based Hot Melt AdhesivesFormulation # Component 4 16 9 17 10 18 11 19 T_(m)/MI Sample D  84/32830 25 — — — — — — Sample I 105/209 — — 30 25 — — — — Sample J  94/368 —— — — 30 25 — — Sample K  78/237 — — — — — — 30 25 Achieve 3866G (1500 —5 — 5 — 5 — 5 (iPP Nucleating Agent) MFR) ESCOREZ ™ 5380 50 50 50 50 5050 50 50 KAYDOL ™ Oil 20 20 20 20 20 20 20 20 IRGANOX ™ 1010 0.25 0.250.25 0.25 0.25 0.25 0.25 0.25 TEMP Viscosity, cps 140° C. 2,550 2,4003,663 2,845 2,410 2,330 2,885 2,755 150° C. 1,805 1,698 2,595 2,0551,698 1,655 2,050 1,955 160° C. 1,318 1,245 1,885 1,505 1,245 1,2131,493 1,415 170° C. 955 940 1,418 1,100 930 913 1,125 1,073 180° C. 770725 1,093 828 713 695 870 828 Tensile Str, psi 57 78 212 184 178 116 9285 Elongation, % 211 234 309 198 360 229 257 237 Substrate Peel Str, pliAl 4.7 3.8 2.4 3.0 3.7 4.1 5.1 6.8 PP 5.4 3.5 5.6 2.9 5.1 1.5 7.4 7.1 PE5.1 5.7 1.1 0.8 3.2 0.4 6.1 4.6 SAFT to Kraft, ° C., (1″ × 65 66 89 9676 82 57 63 1″, 500 g)

TABLE 8 Effect of iPP Nucleating Agent in a SCP based HMA PackagingSystem Formulation # Component 20 21 22 23 24 A 30 30 25 — — ESCORENEUL ™ — — — 30 30 7750 ACHIEVE ™ 3866G 1500 — — 5 — — MFR iPP 400 — — — —5 MFR ESCOREZ ™ 5380 40 50 40 — — ESCOREZ ™ 5400 — — — 55 55 ECR-327 30— 30 — — Wax — 20 — 15 10 IRGANOX ™ 1010 0.25 0.25 0.25 0.25 0.25 TEMPViscosity, cps 150° C. 26,950 17,000 21,600 1,120 2,440 160° C. 18,57512,700 15,325 830 1,750 170° C. 13,800 9,410 11,300 615 1,320 180° C.10,175 7,350 8,425 480 1.015 Tensile Strength, psi 540 210 470 546 527Elongation, % 2,050 2,175 1,760 230 170 Substrate Peel Strength, pli Al10.8 1.35 8.1 0.15 0.1 PP 1.35 0.4 0.2 — — PE 0.5 1.0 1.0 — — SAFT toKraft, ° C. 69 69 96 63 63 (0.5″ × 0.5″, 500 g)

TABLE 9 Evaluation of Propylene-hexene Polymers in a Hot Melt AdhesiveT_(m) (° C.)/Viscosity FORMULATION # (cps @ 190° C.) 25 26 27 28 29 3031 32 Sample # L 101/21,550 30 — — — — — 30 — M — 30 — — 25 — — 30 N — —30 — — — — — O — — — 30 — — — — P — — — — — 80 — — Achieve 3866G (1500MFR) — — — — 5 — — — ESCOREZ ™ 5380 50 50 50 50 50 15 50 50 KAYDOL OIL ™20 20 20 20 20 5 — — PARAFLINT H1 — — — — — — 20 20 IRGANOX ™ 1010 0.250.25 0.25 0.25 0.25 0.25 0.25 0.25 Melt Viscosity, cps 130° C. 3,3552,335 5,388 7,538 2,515 9,575 2,350 2,080 140° C. 2,320 1,605 3,6305,113 1,703 6,650 1,733 1,453 150° C. 1,640 1,140 2,560 3,545 1,2034,800 1,193 1,055 160° C. 1,203 845 1,870 2,580 888 3,540 835 790 170°C. 908 640 1,405 1,930 670 2,710 610 608 180° C. 710 520 1,085 1,485 5182,110 425 478 Tensile Strength, psi 277.2 127.9 302.5 383.5 164.9 1451.8631.2 875 Elongation, % 756.6 492.3 499.6 813.4 368.3 768.3 34.2 13.9Peel Strength, pli Al³ 3.3 3.3 2.97 4.1 2.4 0.19 0.04 0.02 PP⁴ 3.8 2.73.3 5.8 6.5 0.07 0.01 0.01 PE⁵ 0.74 1.64 0.48 2.5 0.88 0.06 0.13 0.08SAFT to Kraft, ° C. 77.2 73.9 83.3 76 87 102.5 91.6 86.4 (1″ × 1″, 500g) ¹Formulation: 22/58/20 blend of VECTOR 4215, ESCOREZ 5400, KAYDOL oil²Formulation: 20/60/20 blend of VECTOR 4461, ESCOREZ 5600, KAYDOL oil³Al = aluminum ⁴PP = polypropylene ⁵PE = polyethylene

Experiments which involve other examples of this invention will now bedescribed. In Examples 5-8, three copolymers and one copolymer blendwere used. The three copolymers are designated below as C1, C2 and C3,while the blend is designated as B1. The blend contains a mixture of acopolymer and an Achieve product, which is a commercially availableisotactic crystalline polypropylene in the weight ratio of 70/30. Therespective ethylene contents of C1, C2, C3 and B1 are 11.5 wt %, 11.8 wt%, 15.7 wt % and 11.0 wt %.

Example 5

In this example, C1 was degraded in a laboratory single screw extruderat 210 NC with Lupersol 101 peroxide as the free radical initiator[2,5-bis(tert-butylperoxy)-2,5-dimethyl-hexane]. Four different levelsof peroxide were used in each experiment (nominally 0.33, 0.67, 1.00 and1.50 wt %), by coating the polymer pellets with the peroxide However,the amount of peroxide that remained on the polymer for degradation wasabout 8 to 10 wt % less than the nominal amounts added. Thecharacterization data for the four degraded samples are shown in Table10. A C1 control sample (C1-0) with no peroxide added but subjected tothe same shear forces in the single screw extruder was used forcomparison purposes in Table 10.

In the experiments with C1, FIG. 1 the addition of 1.5 wt % peroxideraised the MFR of the copolymer to about 1100. Intermediate levels ofperoxide produced copolymer with MFRs having essentially proportionatelevels of MFR. The tests showed that the rise in the MFR corresponded tothe lower Mn of the polymers. The Mn dropped from approximately 87K toabout 25K on the addition of 1.5% peroxide. Intermediate levels ofperoxide provided correspondingly intermediate levels of Mn although thelargest effect on the molecular weight appeared to be the initial amountof copolymer. The data for the change in both the MFR and the Mn areconsistent with the random chain scission reaction in a well mixedreaction. Similar trends were apparent for the variation of the Mw withthe amount of peroxide used. The combination of similar trends in thenumber and weight average of the polymers indicated a relative constancyin the PDI at about 2.0 for the entire range of the degraded polymers.

The mechanical properties of the degraded C1 copolymers of Table 10 areshown below in Table 11. The tensile strength as well as the rise in theextensional modulus due to strain induced crystallization at extensionsbeyond 500% were severely depressed upon degradation. It is contemplatedthat this is due to the smaller chains in the degraded polymers, whichare less capable of crystallizing to form a connected network. It isnoted that the low extensional tensile strength (less than 500%), andthe maximum elongation, were not substantially affected by thedegradation in molecular weight.

TABLE 10 Peroxide Level Mw Mw Mz (with C1) Mn (GPC) (GPC) (LALLS)(LALLS) (wt %) MFR (×1000) (×1000) (×1000) (×1000) PDI — 15.5 86.9 154.8164.5 252.2 1.9 0.33 258 41.9 77.7 79.2 123.5 1.9 0.66 443 35.0 67.770.9 136.2 2.1 1.00 805 29.6 60.6 62.4 105.9 2.1 1.50 1129 25.5 55.055.9 112.4 2.0

TABLE 11 Peroxide Level (with C1) (wt %) Tensile Strength (psi)Elongation (%) — 3642 783 0.33 1846 860 0.66 1767 987 1.00 1518 854 1.501428 882

Example 6

In this example, C2 samples were degraded in a laboratory intensivemixer/extruder at 190 NC-210 NC with the peroxide initiator used inExample 10. Five different levels of peroxide were used (nominally 0.4,0.8, 1.2, 1.6 and 2.0 wt %). Again, the actual levels of peroxide wereslightly lower (about 8-10 wt %) for the experiments that used largeramounts of peroxide due to some material losses during transfer. Acontrol sample (C2-0) was used for comparison purposes, having noperoxide added but subjected to the same shear forces in the singlescrew extruder as the other samples. Mechanical properties of thedegraded polymers were also measured. The results for C2 are reportedbelow in Tables 12 and 13.

The addition of about 1.8 wt % peroxide raised the MFR of the C2copolymer to about 1300. Intermediate levels of peroxide producedessentially proportionate MFR levels. It is contemplated that the risein the MFRs of the samples are correlated to the lower Mn of thepolymers. The Mn dropped from approximately 90K to about 25K on theaddition of 1.8 wt % peroxide. Intermediate levels of peroxide providedintermediate levels of Mn, although the largest effect on the molecularweight appears to be the initial amount of copolymer. The data for thechange in both the MFR and the Mn were consistent with a random chainscission reaction in a well-mixed reaction. Similar trends can be seenbased on the variation of the Mw with the amount of peroxide used. Thecombination of similar trends in the number and weight average of thepolymers indicated a relative constancy in the PDI at about 2.0 for theentire range of the degraded polymers.

As reflected in Table 13 below, the degradation in the molecular weightof the C2 copolymer was reflected in the mechanical properties of thepolymer. The tensile strength as well as the rise in the extensionalmodulus due to strain induced crystallization at extensions beyond 400%are severely depressed upon degradation. This is contemplated to be dueto the smaller chains in the degraded polymers which are less capable ofcrystallizing to form a connected network. It is noted that the lowextensional strength (less than 500%) and the maximum elongation werenot substantially affected by the degradation in molecular weight.

TABLE 12 Peroxide Level Mw Mw Mz (with C2) Mn (GPC) (GPC) (LALLS)(LALLS) (wt %) MFR (×1000) (×1000) (×1000) (×1000) PDI — 13.8 89.8 162.9172.2 252.3 1.9 0.4 364 39.6 72.7 74.4 148.3 1.9 0.8 710 30.9 62.8 60.9105.0 2.0 1.2 884 28.6 60.1 61.2 121.3 2.1 1.6 1005 26.7 58.5 57.1 107.32.1 2.0 1341 24.5 54.9 55.1 133.7 2.2

TABLE 13 Peroxide Level (with C2) (wt %) Tensile Strength (psi)Elongation (%) — 3706 769 0.4 1758 860 0.8 1601 812 1.2 1532 808 1.61441 821 2.0 1384 909

Example 7

In this example, C3 samples were degraded in a laboratory intensivemixer/extruder at 190° C.-210° C. with the peroxide initiator used inExample 10. Five different levels of peroxide were used (nominally 0.4,0.8, 1.2, 1.6 and 2.0 wt %), with actual levels of peroxide beingslightly lower (about 8-10 wt %) for the experiments that used largeamounts of peroxide. A control sample (C3-0) was used for comparisonpurposes, having no peroxide added but subjected to the same shearforces in the single screw extruder as the other samples. Mechanicalproperties of the degraded polymers were also measured. The results forC3 are reported in Tables 14 and 15.

In the experiments with C3, the addition of about 1.8 wt % peroxideraised the MFR of the copolymer to about 1300. Intermediate levels ofperoxide produced essentially proportionate levels of MFR. The rise inthe MFR corresponded to the lower Mn of the polymers. The Mn droppedfrom approximately 95K to about 22K upon addition of 1.8 wt % peroxide.Intermediate levels of peroxide provided intermediate levels of Mnalthough the largest effect on molecular weight appears to be theinitial amount of copolymer. The data for the change in both MFR and Mnare consistent with a random chain scission reaction in a well-mixedreaction. Similar trends were seen for the variation of the Mw with theamount of peroxide used. The combination of similar trends in the numberand weight average of the polymers indicates a relative constancy in thePDI at about 2.0 for the entire range of the degraded polymers.

As reflected in Table 15 below, the degradation in the molecular weightof the C3 copolymer was reflected in the mechanical properties of thepolymer. The tensile strength as well as the rise in the extensionalmodulus due to strain induced crystallization at extensions beyond 400%were severely depressed on degradation. This reached an extreme atperoxide levels of 2.0 wt % where the sample showed elongationsubstantially lower than 500%. This is contemplated to be due to thesmaller chains in the degraded polymers which are less capable ofcrystallizing to form a connected network. It is noted that the lowtensile strength (less than 500%), and the maximum elongation, atintermediate molecular weights were severely affected by the degradationin molecular weight. This suggests that the extreme elastic elongationof copolymers may tend to be limited at low molecular weights (MFRgreater than 1000) for the most amorphous systems.

TABLE 14 Peroxide Level Mw Mw Mz (with C3) Mn (GPC) (GPC) (LALLS)(LALLS) (wt %) MFR (×1000) (×1000) (×1000) (× 1000) PDI — 8.2 94.6 164.4167.8 241.2 1.8 0.4 307 38.7 70.2 71.4 162.4 1.8 0.8 665 30.7 59.9 59.4108.8 1.9 1.2 1062 27.5 53.4 52.9 109.8 1.9 1.6 1110 24.9 52.8 53.7111.9 2.1 2.0 1331 22.9 52.3 52.0 130.8 2.1

TABLE 15 Peroxide Level (with C3) (wt %) Tensile Strength (psi)Elongation (%) — 2219 837 0.4 1013 1185 0.8 709 1189 1.2 455 1211 1.6449 1195 2.0 9 595

Example 8

In this example, B1 was degraded in a single screw extruder at 190°C.-210° C. with the peroxide initiator. Four different levels ofperoxide (nominally 0.33, 0.67, 1.00 and 1.50 wt %) were used for eachexperiment, again, with actual amounts of peroxide being lower. Thecharacterization data for the four degraded samples are shown in Table16 below. Mechanical properties are reported in Table 17. A controlsample (B1-0) was prepared with no peroxide added but which had beensubjected to the same shear forces in the single screw extruder, to beused for comparison purposes.

In the experiments with B1, the addition of 1.5 wt % peroxide raises theMFR of the copolymer to about 1700, as shown in Table 16. This rise inMFR was substantially greater than the rise in MFR for the copolymeralone (C1-C3). In accordance with this invention, it is contemplatedthat this substantially greater MFR increase is due to the preferentialdegradation of the isotactic polypropylene component of the blend.Intermediate levels of peroxide produced correspondingly higher MFRs, asshown in Table 16. The rise of MFR of the B1 samples corresponded to thelower Mn of the polymers. The Mn dropped from approximately 73K to about25K upon addition of 1.5 wt % peroxide. Intermediate levels of peroxideprovided intermediate levels of Mn although the largest effect on themolecular weight appeared to be the initial amount of copolymer. Thedata for the change in both MFR and Mn are consistent with a randomchange scission reaction in a well-mixed reaction. Similar trends areapparent for the variation of the Mw with the amount of peroxide used,The combination of similar trends in the number and weight average ofthe polymers indicates a relative constancy in the PDI at about 2.0 forthe entire range of the degraded polymers.

As reflected in Table 17 below, the degradation in the molecular weightof the MI blend is reflected in its mechanical properties. Both thetensile strength and the rise in extensional modulus due to straininduced crystallization at extensions beyond 500% were severelydepressed upon degradation. This is contemplated to be due to thesmaller chains in the degraded polymers, which are less capable ofcrystallizing to form a connected network. In contrast to the otherdegraded copolymers (C1-C3), the elongation of the blend was severelyretarded by the degradation. Since the degradation of the copolymeralone did not lead to this effect, it is contemplated to be due to theexceptionally low molecular weight of the polypropylene component of theblend. It is noted that the low extensional tensile strength (less then500%), and the maximum elongation, were not substantially affected bythe degradation in molecular weight.

TABLE 16 Peroxide Level Mw Mw Mz (with M1) Mn (GPC) (GPC) (LALLS)(LALLS) (wt %) MFR (×1000) (×1000) (×1000) (×1000) PDI — 33 72.9 139.7147.4 217.3 2.0 0.33 360 38.6 75.8 74.9 131.8 1.9 0.66 883 30 60.1 58.8125.3 1.9 1.00 1087 29.4 57.3 58.8 146.7 2.0 1.50 1736 25.2 52.2 52.8135.4 2.1

TABLE 17 Peroxide Level (with M1) (wt %) Tensile Strength (psi)Elongation (%) — 2373 645 0.33 1700 606 0.66 1586 149 1.00 1596 51 1.501371 45

Example 9

In this example, the MFR values of certain samples were measured inaccordance with ASTM 1238 @ 230° C. All measured Melt Index (MI) valueswere measured at 190° C., with a 2.16 kg weight. DSC was used to measurethe reported melting point values. The samples were formed into a filmannealed for at least 48 hours, and the temperature of the first meltwas measured. The GPC molecular weight values were measured againstpolystyrene standard. Sample I6 was made using 45 grams of EP copolymerdegraded with 0.44 gram of Lupersol 101 in a Brabender. Samples J6 andK6 were synthesized in a reactor using a metallocene catalyst.

TABLE 18 Physical Sample B6 Data Sample A6 Achieve Sample C6 Sample D6Sample E6 Sample F6 Lupersol — — 5.56 8.79 13.3 2.93 101 (g) MFR (mean)10.480 55.140 442.811 804.895 1129.232 359.626 Std. Dev. 0.0188 0.00000.1443 0.2356 0.0000 0.1753 Var. Coeff. 0.1037 0.0000 0.2585 0.23190.0000 0.3867 Shear Rate 25.63 134.70 1081.65 1968.23 2759.64 878.64(sec −1) Viscosity 757 144 18 10 7 22 (Pascals) Brookfield — — 49,20028,000 22,400 60,500 Viscosity (cps @ 190 C.) Measured — — — 361 517 161MI Tm (NC) 76.0 157.0 76.0 78.8 75.5 148.6 Heat of 42.34 64.94 40.0138.50 37.91 29.70 Fusion (J/g) Tc (NC) 13.5 104.7 16.9 22.3 18.6 98.0Heat of 20.19 76.49 18.88 19.85 20.25 37.53 Crystallization (J/g) GPC Mn93,300 — 35,000 29,600 25,500 38,600 Mw 164,900 — 67,900 60,600 55,00075,800 Mz 255,200 — 110,800 107,600 100,700 124,800 Mw/Mn 1.77 — 1.942.05 2.16 1.96

TABLE 19 Physical Data Sample G6 Sample H6 Sample I6 Sample J6 Sample K6Lupersol 101 (g) 5.86 13.3 — — — MFR (mean) 882.609 1735.877 — — — Std.Dev. 0.0000 0.9393 — — — Var. Coeff. 0.000 0.9393 — — — Shear Rate2158.55 4243.34 — 158,400 13,200 (sec −1) Viscosity 9 5 — 54 328(Pascals) Brookfield 25,100 11,700 13,000 — — Viscosity (cps @ 190 C.)Measured MI 281 517 — — — Tm (° C.) 151.2 149.7 — 81 84 Heat of 27.1326.36 — 32.92 24.75 Fusion (J/g) Tc (° C.) 101.1 102.7 — 35 37 Heat of33.27 32.95 — 39.44 33.09 Crystallization (J/g) GPC Mn 30,000 25,200 —58,280 40,065 Mw 60,100 52,200 — 98,131 66,892 Mz 101,200 91,500 —139,588 94,398 Mw/Mn 2.00 2.07 — 1.68 1.67

Example 10

In this example, the polymer samples used in Example 9 were modified byadding various combinations of certain ingredients to form adhesivecompositions, namely, ESCOREZ 5380 (Ingr. #1), KAYDOL (Ingr. #2),PARAFLINT WAX (Ingr. #3) and Irganox 1010 (Ingr. #4). Each modifiedsample was made via extruder breakdown. Certain samples includedisotactic polypropylene in addition to ethylene-propylene copolymer.

The compositions of the samples are shown in Table 20. The first columnidentifies the polymer samples from Example 9 used to make the modifiedSamples A7-H7. Isotactic polypropylene was added to the Samples F6 andG6 ethylene-propylene copolymers, in the amount of about 50 wt % of thetotal polymer weight. The second column indicates the viscosity of eachExample 9 polymer. The third column indicates the estimated Melt Indexof each Example 9 polymer. The remaining columns reflect the weightpercentages of the ingredients for each of Samples A7-H7. It is notedthat Samples A7-D7 have properties considered to be desirable for use indisposable products while Samples E7-H7 have properties desirable forpackaging.

TABLE 20 Ex. 6 Sample Visc. (×000) MI A7 B7 C7 D7 E7 F7 G7 H7 C6 49 14630 — — — 30 — — — F6 60.5 122 — 30 — — — 30 — — D6 28 236 — — 30 — — —30 — G6 25.1 259 — — — 30 — — — 30 Ingr. #1 — — 50 50 50 50 50 50 50 50Ingr. #2 — — 20 20 20 20 — — — — Ingr. #3 — — — — — — 20 20 20 20 Ingr.#4 — —  0.25  0.25  0.25  0.25  0.25  0.25  0.25  0.25

Example 11

In this example, the melt viscosities (in cps) of the Example 10 samples(Samples A7-H7) were measured at different temperatures, and the resultsare reflected in Table 21 below, being identified as Samples A8-H8.Those same samples were also measured for tensile strength andelongation, and the results are shown in Table 22 below.

TABLE 21 Temp (° C.) A8 B8 C8 D8 E8 F8 G8 H8 140 4,513 3,938 2,675 1,4983,805 4,613 2,310 2,340 150 3,175 2,745 1,890 1,060 2,770 3,270 1,6601,683 160 2,335 1,980 1,375 703 2,070 2,450 1,243 1,265 170 1,743 1,4751,043 573 1,555 1,870 948 968 180 1,338 1,145 813 445 1,215 1,440 750758

TABLE 22 Property A8 B8 C8 D8 E8 F8 G8 H8 Tensile 82 100 75 47 646 840683 860 Strength (psi) Elong'n (%) 490 319 237 273 60 40 56 35

Example 12

In this example, the peel strengths (in pli) (pounds per linear inch)were measured for Samples A8-H8, identified below in Table 23, and theresults are reported in Table 14. The term “Al” refers to an aluminumsubstrate. The term “PP” refers to polypropylene. The term “PE” refersto polyethylene. Reported in Table 25 are measured Saft to Kraft valuesin ° C. using 1″×1″ and 500 grams.

TABLE 23 Peel Strength A9 B9 C9 D9 E9 F9 G9 H9 AL 6.1 5.2 5.1 3.6 0.120.10 0.06 0.05 PP 7.9 2.4 6.1 3.7 0.01 0.01 0.01 0.01 PE 7.5 4.1 6.2 4.10.40 0.10 0.21 0.07

TABLE 24 A9 B9 C9 D9 E9 F9 G9 H9 Saft to Kraft 60.9 91.8 56.9 69.3 76.599.5 71.8 86.4

Example 13

In this example, the hot melt adhesive (HMA) performances of varioussamples were measured and compared. In this example, the polymer samplesused in Example 9 were modified by adding various combinations ofcertain ingredients to form adhesive compositions, namely, ESCOREZ 5380(Ingr. #1), KAYDOL (Ingr. #2) and Irganox 1010 (Ingr. #4). Certainsamples included isotactic polypropylene in addition toethylene-propylene copolymer.

The compositions of the samples are shown in Table 25. The first columnidentifies the polymer samples from Example 9 used to make the modifiedSamples A10-G10, except that B6* was a different sample of the same typeof polymer as sample B6 (Achieve), having a melt flow rate of 1500.Isotactic polypropylene was added to the Samples F6 and G6ethylene-propylene copolymers, in the amount of about 50 wt % of thetotal polymer weight. The second column indicates the Brookefieldviscosity (in cps) of each Example 9 polymer. The remaining columnsreflect the weight percentages of the ingredients for each of SamplesA10-G10.

TABLE 25 Ex. 6 Visc. Sample (×000) A10 B10 C10 D10 E10 F10 G10 C6 49 30— — — — — — F6 60.5 — 30 — — — — — D6 28 — — 30 — — — — G6 25.1 — — — 30— — — J6 153 — — — — 30 — — K6 19.0 — — — — — 30 — B6* — — — — — — — 30Ingr. #1 — 50 50 50 50 50 50 50 Ingr. #2 — 20 20 20 20 20 20 20 Ingr. #4—  0.25  0.25  0.25  0.25  0.25  0.25  0.25

Example 14

In this example, the Brookefield viscosities (in cps) of the Example 15samples (Samples A10-G10) were measured at different temperatures, andthe results are reflected in Table 26 below, being identified as SamplesA11-G11. Those same samples were also measured for tensile strength andelongation, and the results are shown in Table 27 below.

TABLE 26 Temp (° C.) A11 B11 C11 D11 E11 F11 G11 140 4,513 3,948 2,6751,498 13,400 2,550 2,400 150 3,175 2,745 1,890 1,060 9,300 1,805 1,698160 2,335 1,980 1,375 703 6,700 1,318 1,245 170 1,743 1,475 1,043 5735,050 905 940 180 1,338 1,145 813 445 3,830 770 725

TABLE 27 Property A11 B11 C11 D11 E11 F11 G11 Tensile 82.36 99.89 74.5846.72 232 57 78 Strength (psi) Elong'n (%) 489.5 318.65 236.87 272.81091 211 234

Example 15

In this example, the peel strengths (in pli) were measured for SamplesA11-G11, identified below as Samples A12-G12, and the results arereported in Table 28. Reported in Table 29 are measured Saft to Kraftvalues in NC using 1″×1″ and 500 grams.

TABLE 28 Peel Strength A12 B12 C12 D12 E12 F12 G12 AL 6.1 5.2 5.1 3.64.2 4.7 3.8 PP 7.9 2.4 6.1 3.7 6.9 5.4 3.5 PE 7.5 4.1 6.2 4.1 2.2 5.15.7

TABLE 29 A12 B12 C12 D12 E12 F12 G12 Saft to Kraft 60.9 91.8 56.9 69.378 65 66

Example 16

In this example, modified samples were formulated, using certainpolymers from Example 9 (as indicated) along with other polymer samplesand ingredients, all identified as “components” below. Component 1-13 isESCORENE UL7720 Component 2-13 is ESCOREZ 5400, Component 3-13 isESCOREZ 5600, Component 4-13 is ECR 187, Component 5-13 is Paraflint H1,Component 6-13 is Sample E6 (from Example 9), Component 7-13 is SampleH6 (from Example 9), Component 8-13 is Sample I6 (from Example 9) andComponent 9-13 is Irganox 1010 (an antioxidant). The weight percentagesof the various components are identified in Table 30. Various propertiesof Samples A13-H13 were then measured, and the results are reported inTable 31.

TABLE 30 Comp. A13 B13 C13 D13 E13 F13 G13 H13 1-13 30 30 30 — — — — —2-13 22.5 22.5 22.5 — — — — — 3-13 22.5 22.5 22.5 — — — — — 4-13 — — —70 70 — 60 60 5-13 25 — — — — — 10 10 6-13 — 25 — 30 — — — — 7-13 — — 25— 30 — 30 — 8-13 — — — — — — — 30 9-13  1  1  1  1  1 —  1  1

TABLE 31 Prop. A13 B13 C13 D13 E13 F13 G13 H13 Visc @ 325 F. 1,01517,475 15,350 7,025 6,238 — 1,845 2,260 Fiber Tear Substrate CohesiveFiber tear Substrate Substrate — 50% Substrate (%) failure failure 80%.75%. failure. failure. substrate failure. Fiber tear Fiber tear CohesiveFiber tear Fiber tear failure. tear 100% 100% 20%. Base failure 100%100% 50% fiber failure. tear. SAFT (deg F.) 186 148 149 207 231 — 206204 Tensile 591 407 426 617 548 — 257 330 Strength (psi) Tensile 2281855 690 0.3 Snapped — 20 2.67 Elong'n (%) Observations — — — BrittleBrittle Brittle Brittle

1. An adhesive composition comprising: a semi-crystalline copolymer ofpropylene and at least one comonomer selected from the group consistingof ethylene and C₄ to C₂₀ α-olefins having a propylene content ofgreater than 65 mole percent and a comonomer content of less than 15mole percent; wherein the copolymer has a weight average molecularweight (Mw) from about 15,000 to about 200,000; a MFR of greater than250 dg/min.; and a weight average molecular weight/number averagemolecular weight ratio (Mw/Mn) of between 1.8 to
 5. 2. The adhesivecomposition of claim 1 wherein the semi-crystalline copolymer has aweight average/number average molecular weight (Mw/Mn) of 1.8 to
 3. 3.The adhesive composition of claim 1 wherein the semi-crystallinecopolymer has a weight average/number average molecular weight (Mw/Mn)of approximately
 2. 4. The adhesive composition of claim 1 wherein thesemi-crystalline copolymer has a melt index (MI) from about 7 dg/min toabout 3000 dg/min as measured by ASTM D1238(B).
 5. The adhesivecomposition of claim 1 having an MFR of at least about 500 dg/min. at230° C.
 6. The adhesive composition of claim 1 wherein thesemi-crystalline copolymer has a propylene content greater than 73 molepercent.
 7. The adhesive composition of claim 1 wherein thesemi-crystalline copolymer has a melt index of from about 20 dg/min toabout 900 dg/min as measured by ASTM D 1238(B).
 8. The adhesivecomposition of claim 1 wherein the semi-crystalline copolymer has arandom comonomer sequence distribution.
 9. The adhesive composition ofclaim 1 wherein the copolymer is a branched random copolymer.
 10. Theadhesive composition of claim 1 wherein the semi-crystalline copolymercomprises a heat of fusion from about 30 to about 80 J/g as determinedby DSC.
 11. The adhesive composition of claim 1 wherein thesemi-crystalline copolymer comprises isotactic polypropylene sequences.12. The adhesive composition of claim 1 wherein said comonomer is1-hexene.
 13. The adhesive composition of claim 1 further comprising awax.
 14. The adhesive composition of claim 1 further comprising at leastone or more additives selected from the group consisting of a tackifierand an antioxidant.
 15. The adhesive composition of claim 1 wherein thesemi-crystalline copolymer has a weight average molecular weight (Mw) offrom about 50,000 to about 150,000.
 16. An adhesive compositioncomprising: a semi-crystalline metallocene catalyst polymerizationderived copolymer of propylene and hexene wherein the copolymer has apropylene content of at least 65 mole percent and a hexene content ofless than 15 mole percent, wherein said propylene has a polypropylenecrystallinity from 2% to 65%, and the copolymer has a weight averagemolecular weight ratio of (Mw/Mn) of between 1.8 to 3.